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Sample records for nanocrystalline ni-fe alloy

  1. Microstructure Evolution during Cold Rolling in a Nanocrystalline Ni-Fe Alloy Determined by Synchrotron X-ray Diffraction

    SciTech Connect

    Li, Li; Ungar, Prof Tomas; Wang, Y. D.; Morris, James R; Tichy, G.; Lendvai, J.; Wang, Y. L.; Ren, Y.; Choo, H.; Liaw, Peter K

    2009-01-01

    Stress softening after cold rolling is observed in an electrodeposited nanocrystalline Ni-Fe alloy. The grain-size distribution becomes much broader after the cold rolling. Microstructure changes, though moderate, such as simultaneously decreased dislocation and twin densities with grain growth during cold rolling, are systematically proved by synchrotron high-energy X-ray diffraction, and transmission-electron microscopy and differential-scanning calorimetry (DSC). The amorphous fractions in the form of grain boundaries are evidenced by the diffuse-background scatterings and large DSC values. Partial dislocation separation calculation, a dislocation mean free path and annihilation model, and texture development together reveal that the current nanocrystalline Ni-Fe alloy exhibits the combined behavior of perfect dislocation slip and grain-boundary mediated deformation.

  2. Dislocation density evolution during high pressure torsion of a nanocrystalline Ni-Fe alloy

    SciTech Connect

    Li, Hongqi; Wang, Y B; Ho, J C; Cao, Y; Liao, X Z; Ringer, S P; Zhu, Y T; Zhao, Y H; Lavernia, E J

    2009-01-01

    High-pressure torsion (HPT) induced dislocation density evolution in a nanocrystalline Ni-20wt.%Fe alloy was investigated using X-ray diffraction and transmission electron microscopy. Results suggest that the dislocation density evolution is different from that in coarse-grained materials. An HPT process first reduces the dislocation density within nanocrystalline grains and produces a large number of dislocations located at small-angle sub grain boundaries that are formed via grain rotation and coalescence. Continuing the deformation process eliminates the sub grain boundaries but significantly increases the dislocation density in grains. This phenomenon provides an explanation of the mechanical behavior of some nanostructured materials.

  3. Shear-Coupled Grain Growth and Texture Development in a Nanocrystalline Ni-Fe Alloy during Cold Rolling

    NASA Astrophysics Data System (ADS)

    Li, Li; Ungár, Tamás; Toth, Laszlo S.; Skrotzki, Werner; Wang, Yan Dong; Ren, Yang; Choo, Hahn; Fogarassy, Zsolt; Zhou, X. T.; Liaw, Peter K.

    2016-09-01

    The evolution of texture, grain size, grain shape, dislocation, and twin density has been determined by synchrotron X-ray diffraction and line profile analysis in a nanocrystalline Ni-Fe alloy after cold rolling along different directions related to the initial fiber and the long axis of grains. The texture evolution has been simulated by the Taylor-type relaxed-constraints viscoplastic polycrystal model. The simulations were based on the activity of partial dislocations in correlation with the experimental results of dislocation density determination. The concept of stress-induced shear coupling is supported and strengthened by both the texture simulations and the experimentally determined evolution of the microstructure parameters. Grain growth and texture evolution are shown to proceed by the shear coupling mechanism supported by dislocation activity as long as the grain size is not smaller than about 20 nm.

  4. Mechanism of grain growth during severe plastic deformation of a nanocrystalline Ni-Fe alloy

    SciTech Connect

    Li, Hongqi; Wang, Y B; Ho, J C; Liao, X Z; Zhu, Y T; Ringer, S P

    2009-01-01

    Deformation induced grain growth has been widely reported in nanocrystalline materials. However, the grain growth mechanism remains an open question. This study applies high-pressure torsion to severely deform bulk nanocrystalline Ni-20 wt % Fe disks and uses transmission electron microscopy to characterize the grain growth process. Our results provide solid evidence suggesting that high pressure torsion induced grain growth is achieved primarily via grain rotation for grains much smaller than 100 nm. Dislocations are mainly seen at small-angle subgrain boundaries during the grain growth process but are seen everywhere in grains after the grains have grown large.

  5. Structure modulation driven by cyclic deformation in nanocrystalline NiFe

    SciTech Connect

    Cheng, Sheng; Wang, Xun-Li; Zhao, Yh; Wang, Yinmin; Liaw, Peter K; Lavernia, Ej

    2010-01-01

    Theoretical modeling suggests that the grain size remains unchanged during fatigue crack growth in nanocrystalline metals. Here we demonstrate that a modulated structure is generated in a nanocrystalline Ni-Fe alloy under cyclic deformation. Substantial grain coarsening and loss of growth twins are observed in the path of fatigue cracks, while the grains away from the cracks remain largely unaffected. Statistical analyses suggest that the grain coarsening is realized through the grain lattice rotation and coalescence and the loss of growth twins may be related to the detwinning process near crack tip.

  6. Cyclic voltammetric study of Co-Ni-Fe alloys electrodeposition in sulfate medium

    SciTech Connect

    Hanafi, I.; Daud, A. R.; Radiman, S.

    2013-11-27

    Electrochemical technique has been used to study the electrodeposition of cobalt, nickel, iron and Co-Ni-Fe alloy on indium tin oxide (ITO) coated glass substrate. To obtain the nucleation mechanism, cyclic voltammetry is used to characterize the Co-Ni-Fe system. The scanning rate effect on the deposition process was investigated. Deposition of single metal occurs at potential values more positive than that estimated stability potential. Based on the cyclic voltammetry results, the electrodeposition of cobalt, nickel, iron and Co-Ni-Fe alloy clearly show that the process of diffusion occurs is controlled by the typical nucleation mechanism.

  7. Abnormal magnetization behaviors in Sm-Ni-Fe-Cu alloys

    NASA Astrophysics Data System (ADS)

    Yang, W. Y.; Zhang, Y. F.; Zhao, H.; Chen, G. F.; Zhang, Y.; Du, H. L.; Liu, S. Q.; Wang, C. S.; Han, J. Z.; Yang, Y. C.; Yang, J. B.

    2016-06-01

    The magnetization behaviors in Sm-Ni-Fe-Cu alloys at low temperatures have been investigated. It was found that the hysteresis loops show wasp-waisted character at low temperatures, which has been proved to be related to the existence of multi-phases, the Fe/Ni soft magnetic phases and the CaCu5-type hard magnetic phase. A smooth-jump behavior of the magnetization is observed at T>5 K, whereas a step-like magnetization process appears at T<5 K. The CaCu5-type phase is responsible for such abnormal magnetization behavior. The magnetic moment reversal model with thermal activation is used to explain the relation of the critical magnetic field (Hcm) to the temperature (T>5 K). The reversal of the moment direction has to cross over an energy barrier of about 6.6×10-15 erg. The step-like jumps of the magnetization below 5 K is proposed to be resulted from a sharp increase of the sample temperature under the heat released by the irreversible domain wall motion.

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

    NASA Astrophysics Data System (ADS)

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

    We have investigated CoNiFe and CoNiFe-C electrodeposited by pulse reverse plating (PRP) and direct current (DC) techniques. CoNiFe(PRP) films with composition Co 59.4Fe 27.7Ni 12.8 show coercivity of 95 A m -1 (1.2 Oe) and magnetization saturation flux ( μ0Ms) of 1.8 T. Resistivity of CoNiFe (PRP) is about 24 μΩ cm and permeability remains almost constant μr' ˜475 up to 30 MHz with a quality factor ( Q) larger than 10. Additionally, the permeability spectra analysis shows that CoNiFe exhibits a classical eddy current loss at zero bias field and ferromagnetic resonance (FMR) when biased with 0.05 T. Furthermore, a crossover between eddy current and FMR loss is observed for CoNiFe-PRP when baised with 0.05 T. DC and PRP plated CoNiFe-C, which have resistivity and permeability of 85, 38 μΩ cm, μr'=165 and 35 with Q>10 up to 320 MHz, respectively, showed only ferromagnetic resonance losses. The ferromagnetic resonance peaks in CoNiFe and CoNiFe-C are broad and resembles a Gaussian distribution of FMR frequencies. The incorporation of C to CoNiFe reduces eddy current loss, but also reduces the FMR frequency.

  9. A NiFeCu alloy anode catalyst for direct-methane solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Zhu, Huaiyu; Yang, Guangming; Park, Hee Jung; Jung, Doh Won; Kwak, Chan; Shao, Zongping

    2014-07-01

    In this study, a new anode catalyst based on a NiFeCu alloy is investigated for use in direct-methane solid oxide fuel cells (SOFCs). The influence of the conductive copper introduced into the anode catalyst layer on the performance of the SOFCs is systematically studied. The catalytic activity for partial oxidation of methane and coking resistance tests are proposed with various anode catalyst layer materials prepared using different methods, including glycine nitrate process (GNP), physical mixing (PM) and impregnation (IMP). The surface conductivity tests indicate that the conductivities of the NiFe-ZrO2/Cu (PM) and NiFe-ZrO2/Cu (IMP) catalysts are considerably greater than that of NiFe-ZrO2/Cu (GNP), which is consistent with the SEM results. Among the three preparation methods, the cell containing the NiFe-ZrO2/Cu (IMP) catalyst layer performs best on CH4-O2 fuel, especially under reduced temperatures, because the coking resistance should be considered in real fuel cell conditions. The cell containing the NiFe-ZrO2/Cu (IMP) catalyst layer also delivers an excellent operational stability using CH4-O2 fuel for 100 h without any signs of decay. In summary, this work provides new alternative anode catalytic materials to accelerate the commercialization of SOFC technology.

  10. Magnetic properties of pulse-reverse electrodeposited nanocrystalline NiFe/Cu composite wires in relation to the anodic current

    NASA Astrophysics Data System (ADS)

    Seet, H. L.; Li, X. P.; Lee, K. S.; Chia, H. Y.; Zheng, H. M.; Ng, W. C.

    2007-12-01

    Ni80Fe20/Cu composite wires were developed using the pulse-reverse electrodeposition technique with the cathodic (positive) current Ic fixed at 1 mA and the anodic (negative) current IA varied from 10 to 90% of Ic. The relationship between the magnetic properties of pulse reverse electrodeposited nanocrystalline NiFe/Cu composite wires and the anodic current was investigated. The results showed that the smaller the magnitude of the anodic current, the smaller was the average nanocrystalline grain size of the deposited material and the better was the uniformity of the surface, and consequently, the better the magnetic properties.

  11. PVD synthesis and high-throughput property characterization of NiFeCr alloy libraries

    SciTech Connect

    Rar, A.; Frafjord, J. J.; Fowlkes, Jason D.; Specht, E. D.; Rack, P. D.; Santella, M. L.; Bei, H.; George, E. P.; Pharr, G. M.

    2004-12-16

    Three methods of alloy library synthesis, thick-layer deposition followed by interdiffusion, composition-spread codeposition and electron-beam melting of thick deposited layers, have been applied to Ni-Fe-Cr ternary and Ni-Cr binary alloys. Structural XRD mapping and mechanical characterization by means of nanoindentation have been used to characterize the properties of the libraries. The library synthesis methods are compared from the point of view of the structural and mechanical information they can provide.

  12. Martensite Transformation and Magnetic Properties of Ni-Fe-Ga Heusler Alloys

    NASA Astrophysics Data System (ADS)

    Nath, Hrusikesh; Phanikumar, Gandham

    2015-11-01

    Compositional instability and phase formation in Ni-Fe-Ga Heusler alloys are investigated. The alloys are synthesized into two-phase microstructure. Their structures are identified as fcc and L 21, respectively. The γ-phase formation could be suppressed with higher Ga-content in the alloy as Ga stabilizes austenite phase, but Ga lowers the martensite transformation temperature. The increase of Fe content improves the magnetization value and the increase of Ni from 52 to 55 at. pct raises the martensite transformation temperature from 216 K to 357 K (-57 °C to 84 °C). Magnetic properties and martensitic transformation behavior in Ni-Fe-Ga Heusler alloys follow opposite trends, while Ni replaces either Fe or Ga, whereas they follow similar trends, while Fe replaces Ga. Modulated martensite structure has low twinning stress and high magneto crystalline anisotropic properties. Thus, the observation of 10- and 14 M-modulated martensite structures in the studied Ni-Fe-Ga Heusler alloys is beneficial for shape memory applications. The interdependency of alloy composition, phase formation, magnetic properties, and martensite transformation are discussed.

  13. 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.

  14. 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. PMID:23809618

  15. The energetics and electronic origins for atomic long- and short-range order in Ni-Fe invar alloys

    SciTech Connect

    Johnson, D.D.; Shelton, W.A.

    1996-12-31

    States of magnetic and compositional order are strongly coupled in many magnetic alloys, with Ni-Fe Invar being the most celebrated example. Results of an electronic-based method that addresses compositional and magnetic disorder, as well as atomic short-range order and energetics, are discussed. This allows a system-dependent microscopic understanding of the interplay of chemical, magnetic, and displacive effects, and a direct comparison to diffuse scattering experiments. Discussion is in context of total-energy calculations for various magnetic states in chemically disordered and ordered Ni- Fe alloys, emphasizing the importance of exchange-splitting and the implication for phase stability in Ni-Fe system.

  16. Nanocrystalline Pd:NiFe2O4 thin films: A selective ethanol gas sensor

    NASA Astrophysics Data System (ADS)

    Rao, Pratibha; Godbole, R. V.; Bhagwat, Sunita

    2016-10-01

    In this work, Pd:NiFe2O4 thin films were investigated for the detection of reducing gases. These films were fabricated using spray pyrolysis technique and characterized using X-ray diffraction (XRD) to confirm the crystal structure. The surface morphology was studied using scanning electron microscopy (SEM). Magnetization measurements were carried out using SQUID VSM, which shows ferrimagnetic behavior of the samples. These thin film sensors were tested against methanol, ethanol, hydrogen sulfide and liquid petroleum gas, where they were found to be more selective to ethanol. The fabricated thin film sensors exhibited linear response signal for all the gases with concentrations up to 5 w/o Pd. Reduction in optimum operating temperature and enhancement in response was also observed. Pd:NiFe2O4 thin films exhibited faster response and recovery characteristic. These sensors have potential for industrial applications because of their long-term stability, low power requirement and low production cost.

  17. Slip transfer and dislocation nucleation processes in multiphase ordered Ni-Fe-Al alloys

    SciTech Connect

    Misra, A.; Bibala

    1999-04-01

    Directionally solidified (DS) alloys with the nominal composition Ni-30 at. pct Fe-20 at. pct Al having eutectic microstructures were used to study slip transfer across interphase boundaries and dislocation nucleation at the interfacial steps. The slip transfer from the ductile second phase, {gamma}(fcc) containing ordered {gamma}{prime}(L1{sub 2}) precipitates, to the ordered {beta}(B2) phase and the generation of dislocations at the interface steps were interpreted using the mechanisms proposed for similar processes involving grain boundaries in polycrystalline single-phase materials. The criteria for predicting the slip systems activated as a result of slip transfer across grain boundaries were found to be applicable for interphase boundaries in the multiphase ordered Ni-Fe-Al alloys. The potential of tailoring the microstructures and interfaces to promote slip transfer and thereby enhance the intrinsic ductility of dislocation-density-limited intermetallic alloys is discussed.

  18. Spin-driven ordering of Cr in the equiatomic high entropy alloy NiFeCrCo

    SciTech Connect

    Niu, C.; Zaddach, A. J.; Oni, A. A.; Sang, X.; LeBeau, J. M.; Koch, C. C.; Irving, D. L.; Hurt, J. W.

    2015-04-20

    Spin-driven ordering of Cr in an equiatomic fcc NiFeCrCo high entropy alloy (HEA) was predicted by first-principles calculations. Ordering of Cr is driven by the reduction in energy realized by surrounding anti-ferromagnetic Cr with ferromagnetic Ni, Fe, and Co in an alloyed L1{sub 2} structure. The fully Cr-ordered alloyed L1{sub 2} phase was predicted to have a magnetic moment that is 36% of that for the magnetically frustrated random solid solution. Three samples were synthesized by milling or casting/annealing. The cast/annealed sample was found to have a low temperature magnetic moment that is 44% of the moment in the milled sample, which is consistent with theoretical predictions for ordering. Scanning transmission electron microscopy measurements were performed and the presence of ordered nano-domains in cast/annealed samples throughout the equiatomic NiFeCrCo HEA was identified.

  19. Magnetic Behavior of Ni-Fe Core-Shell and Alloy Nanowires

    NASA Astrophysics Data System (ADS)

    Tripathy, Jagnyaseni; Vargas, Jose; Spinu, Leonard; Wiley, John

    2013-03-01

    Template assisted synthesis was used to fabricate a series of Ni-Fe core-shell and alloy nanowires. By controlling reaction conditions as well as pore structure, both systems could be targeted and magnetic properties followed as a function of architectures. In the core-shell structure coercivity increases with decrease in shell thickness while for the alloys, coercivity squareness improve with increase pore diameter. Details on the systematic studies of these materials will be presented in terms of hysteretic measurements, including first order reversal curves (FORC), and FMR data. Magnetic variation as a function of structure and nanowire aspect ratios will be presented and the origins of these behaviors discussed. Advanced Material Research Institute

  20. Stress Corrosion Cracking of Ni-Fe-Cr Alloys Relevant to Nuclear Power Plants

    NASA Astrophysics Data System (ADS)

    Persaud, Suraj

    Stress corrosion cracking (SCC) of Ni-Fe-Cr alloys and weld metals was investigated in simulated environments representative of high temperature water used in the primary and secondary circuits of nuclear power plants. The mechanism of primary water SCC (PWSCC) was studied in Alloys 600, 690, 800 and Alloy 82 dissimilar metal welds using the internal oxidation model as a guide. Initial experiments were carried out in a 480°C hydrogenated steam environment considered to simulate high temperature reducing primary water. Ni alloys underwent classical internal oxidation intragranularly resulting in the expulsion of the solvent metal, Ni, to the surface. Selective intergranular oxidation of Cr in Alloy 600 resulted in embrittlement, while other alloys were resistant owing to their increased Cr contents. Atom probe tomography was used to determine the short-circuit diffusion path used for Ni expulsion at a sub-nanometer scale, which was concluded to be oxide-metal interfaces. Further exposures of Alloys 600 and 800 were done in 315°C simulated primary water and intergranular oxidation tendency was comparable to 480°C hydrogenated steam. Secondary side work involved SCC experiments and electrochemical measurements, which were done at 315°C in acid sulfate solutions. Alloy 800 C-rings were found to undergo acid sulfate SCC (AcSCC) to a depth of up to 300 microm in 0.55 M sulfate solution at pH 4.3. A focused-ion beam was used to extract a crack tip from a C-ring and high resolution analytical electron microscopy revealed a duplex oxide structure and the presence of sulfur. Electrochemical measurements were taken on Ni alloys to complement crack tip analysis; sulfate was concluded to be the aggressive anion in mixed sulfate and chloride systems. Results from electrochemical measurements and crack tip analysis suggested a slip dissolution-type mechanism to explain AcSCC in Ni alloys.

  1. Research on Process and Microstructure Formation of W-Ni-Fe Alloy Fabricated by Selective Laser Melting

    NASA Astrophysics Data System (ADS)

    Zhang, Danqing; Cai, Qizhou; Liu, Jinhui; Li, Ruidi

    2011-08-01

    W-Ni-Fe alloys are important materials for many practical applications; however, at present, they are usually fabricated by conventional powder metallurgy techniques, which is difficult in fabrication with complex shapes. In this work, a selective laser melting (SLM) processing method was developed for fabricating W-Ni-Fe alloys parts. A process map was obtained for selection of proper laser parameters by optimizing processing conditions. Microstructures of laser fabricated samples in different laser energy inputs were investigated. There are two coexisting forming mechanisms in the SLM process: (i) liquid phase sintering (LPS) with full melting of Ni and Fe powders but non-melting of W powders and (ii) melting/solidification with full melting of W powders. Moreover, with increasing laser energy, a transition trend of forming mechanism from LPS to full melting/solidification can be observed.

  2. Interphase boundary precipitation in liquid phase sintered W-Ni-Fe and W-Ni-Cu alloys

    SciTech Connect

    Muddle, B.C.

    1984-06-01

    A serious potential of embrittlement in liquid-phase sintered, tungsten-based heavy alloys is related to the precipitation of a brittle third phase along tungsten-matrix interphase boundaries. The present investigation is concerned with the identification of the phase observed to form at the tungsten-matrix interphase within a commercial W-Ni-Fe alloy containing a weight fraction Ni:Fe of 1:1. A severely embrittled sample of a commercial W-4.5 wt pct Ni-4.5 wt pct Fe alloy and heat treated specimens of a W-7.2 wt pct Ni-2.4 wt pct Cu alloy were used in a study of interphase boundary precipitation. It was possible to identify the embrittling interphase boundary precipitate formed in commercial W-4.5 wt pct Ni-4.5 wt pct Fe alloy. The interphase boundary precipitation of an intermetallic phase in W-7.2 wt pct Ni-2.4 wt pct Cu alloy under controlled conditions of heat treatment could also be confirmed. 34 references.

  3. Room-temperature deformation behavior of directionally solidified multiphase Ni-Fe-Al alloys

    SciTech Connect

    Misra, A.; Gibala, R.

    1997-03-01

    Directionally solidified (DS) {beta} + ({gamma} + {gamma}{prime}) Ni-Fe-Al alloys have been used to investigate the effect of a ductile second phase on the room-temperature mechanical behavior of a brittle <001>-oriented {beta} (B2) phase. The ductile phase in the composite consisted of a fine distribution of ordered {gamma}{prime} precipitates in a {gamma} (fcc) matrix. Three microstructures were studied: 100 pct lamellar/rod, lamellar + Proeutectic {beta}, and discontinuous {gamma}. The {beta} matrix in the latter two microstructures contained fine-scale bcc precipitates formed due to spinodal decomposition. Room-temperature tensile ductilities as high as 12 pct and fracture toughness (K{sub Q}) of 30.4 MPa {radical}m were observed in the 100 pct lamellar/rod microstructure. Observations of slip traces and dislocation substructures indicated that a substantial portion of the ductility was a result of slip transfer from the ductile phase to the brittle matrix. This slip transfer was facilitated by the Kurdjumov-Sachs (KS) orientation relationship between the two phases and the strong interphase interface which showed no decohesion during deformation. In microstructures which show higher values of tensile ductility and fracture toughness, <100> slip was seen in the {beta} phase, whereas <111> slip was seen in the {beta} phase in the microstructure which showed limited ductility. The high ductility and toughness are explained in terms of increased mobile dislocation density afforded by interface constraint. The effect of extrinsic toughening mechanisms on enhancing the ductility or toughness is secondary to that of slip transfer.

  4. Electromagnetic properties of core-shell particles by way of electroless Ni-Fe-P alloy plating on flake-shaped diatomite

    NASA Astrophysics Data System (ADS)

    Zhang, Deyuan; Yuan, Liming; Lan, Mingming; Hu, Yanyan; Cai, Jun; Zhang, Wenqiang; Li, Haiyang

    2013-11-01

    Flake-shaped diatomite particles coated by Ni-Fe-P alloy were prepared by electroless plating technique and processed by heat treatment. The samples were characterized by SEM, EDS and XRD. The results indicated that the magnetic diatomite particles had continuous and homogeneous Ni-Fe-P coating, and the phase constitution of the Ni-Fe-P coating was transformed from an amorphous structure to a crystalline structure during heat treatment. The measured electromagnetic parameters and the calculated reflection loss suggested that heat treatment was able to enhance the microwave absorption performance of the paraffin wax based composites. In a word, the Ni-Fe-P coated diatomite particle obtained in this paper is a promising candidate for lightweight microwave absorbing inclusions.

  5. Structure-Property Relationship of Cu-Al-Ni-Fe Shape Memory Alloys in Different Quenching Media

    NASA Astrophysics Data System (ADS)

    Saud, Safaa N.; Hamzah, E.; Abubakar, T.; Farahany, S.

    2014-01-01

    This paper presents the effects of heat treatments using various quenching media on the phase transformation parameters and microstructure parameters. The effects of different quenching methods, step-quenched and up-quenched, in various media were evaluated by using differential scanning calorimetry, field emission electron microscopy, energy-dispersive spectrometry, atomic force microscopy, x-ray diffraction, and Vicker's hardness. The variations of the structure and properties of Cu-Al-Ni-Fe shape memory alloys were linked to the variations of morphology, type, and stabilization of the obtained phase. From the DSC results, the use of ice water as a quenching medium produced the highest transformation temperatures, while a brine solution-quenching medium resulted in the highest change of the entropy and enthalpy. Additionally, it was found that the best grain refinement was observed through the use of an oil-quenching medium, due to its high cooling rate.

  6. A-site-deficiency facilitated in situ growth of bimetallic Ni-Fe nano-alloys: a novel coking-tolerant fuel cell anode catalyst

    NASA Astrophysics Data System (ADS)

    Sun, Yi-Fei; Li, Jian-Hui; Cui, Lin; Hua, Bin; Cui, Shao-Hua; Li, Jian; Luo, Jing-Li

    2015-06-01

    To date, most investigations of Ni-Fe bimetallic catalysts for solid oxide fuel cells (SOFCs) have focused on materials with micro-scale particle sizes, which severely restrict their catalytic activity. In this study, we fabricated a Ni- and/or Fe-doped A-site-deficient LaSrCrO3 perovskite (A-LSC) bimetallic anode material on which the in situ exsolution of uniformly dispersed nano Ni, Fe and Ni-Fe alloy with an average particle size of 25 to 30 nm was facilitated by the introduction of A-site deficiency under a reducing atmosphere. The dopants were shown to significantly enhance the electrical conductivity of the material by many orders of magnitude. Further characterization of the bimetallic material showed that the addition of Fe changed the reduction behavior and increased the amount of oxygen vacancies in the material. Fuel cell performance tests demonstrated that the prepared bimetallic anode catalyst with a highly catalytically active nano Ni-Fe alloy promoted the electrochemical performance in 5000 ppm H2S-syngas and improved the carbon deposition resistance compared to a monometallic anode catalyst.

  7. N-doped graphene layers encapsulated NiFe alloy nanoparticles derived from MOFs with superior electrochemical performance for oxygen evolution reaction

    NASA Astrophysics Data System (ADS)

    Feng, Yi; Yu, Xin-Yao; Paik, Ungyu

    2016-09-01

    Water splitting, an efficient approach for hydrogen production, is often hindered by unfavorable kinetics of oxygen evolution reaction (OER). In order to reduce the overpotential, noble metal oxides-based electrocatalysts like RuO2 and IrO2 are usually utilized. However, due to their scarcity, the development of cost-effective non-precious OER electrocatalysts with high efficiency and good stability is urgently required. Herein, we report a facile one-step annealing of metal-organic frameworks (MOFs) strategy to synthesize N-doped graphene layers encapsulated NiFe alloy nanoparticles (NiFe@C). Through tuning the nanoparticle size and calcination temperature, NiFe@C with an average size of around 16 nm obtained at 700 °C exhibits superior OER performance with an overpotential of only 281 mV at 10 mA cm‑2 and high durability. The facile synthesis method and excellent electrochemical performance show great potential of NiFe@C in replacing the precious metal-based electrocatalysts in the OER.

  8. N-doped graphene layers encapsulated NiFe alloy nanoparticles derived from MOFs with superior electrochemical performance for oxygen evolution reaction

    PubMed Central

    Feng, Yi; Yu, Xin-Yao; Paik, Ungyu

    2016-01-01

    Water splitting, an efficient approach for hydrogen production, is often hindered by unfavorable kinetics of oxygen evolution reaction (OER). In order to reduce the overpotential, noble metal oxides-based electrocatalysts like RuO2 and IrO2 are usually utilized. However, due to their scarcity, the development of cost-effective non-precious OER electrocatalysts with high efficiency and good stability is urgently required. Herein, we report a facile one-step annealing of metal-organic frameworks (MOFs) strategy to synthesize N-doped graphene layers encapsulated NiFe alloy nanoparticles (NiFe@C). Through tuning the nanoparticle size and calcination temperature, NiFe@C with an average size of around 16 nm obtained at 700 °C exhibits superior OER performance with an overpotential of only 281 mV at 10 mA cm−2 and high durability. The facile synthesis method and excellent electrochemical performance show great potential of NiFe@C in replacing the precious metal-based electrocatalysts in the OER. PMID:27658968

  9. Effect of cathode vibration and heat treatment on electromagnetic properties of flake-shaped diatomite coated with Ni-Fe alloy by electroplating

    NASA Astrophysics Data System (ADS)

    Lan, Mingming; Li, Huiqin; Huang, Weihua; Xu, Guangyin; Li, Yan

    2015-03-01

    In this paper, flake-shaped diatomite particles were used as forming templates for the fabrication of the ferromagnetic functional fillers by way of electroplating Ni-Fe alloy method. The effects of cathode vibration frequency on the content of Ni-Fe alloy in the coating and the surface morphologies of the coatings were evaluated. The electromagnetic properties of the coated diatomite particles before and after heat treatment were also investigated in detail. The results show that the core-shell flake-shaped diatomite particles with high content of Ni-Fe alloy and good surface qualities of the coatings can be obtained by adjusting cathode vibration frequency. The coated diatomite particles with heat treatment filled paraffin wax composites exhibit a superior microwave absorbing and electromagnetic properties compared to the non-heat treated samples. Additionally, the peaks of reflection loss are found to be able to shift to lower frequency by the heat treatment process, which indicates the heat treatment can adjust microwave absorbing frequency band.

  10. Soft magnetic Ni-Fe and Co-Fe alloys - some physical and metallurgical aspects

    NASA Astrophysics Data System (ADS)

    Pfeifer, F.; Radeloff, C.

    1980-04-01

    The diversity of properties of soft magnetic alloys has been vastly increased in recent years. In this paper a number of the physical and metallurgical aspects are discussed, particularly those which influence the properties of the technically important nickel-iron alloys. These include the composition of the alloy, isotropic and anisotropic ordering processes, the microstructure, textures, non-magnetic inclusions and precipitation processes. These factors are, on the other hand, partially determined by manufacturing parameters such as the type of melting, the degree of cold rolling and the heat treatment.

  11. Physical properties of Kx(Ni,Fe)2-ySe2 single crystal alloys1

    NASA Astrophysics Data System (ADS)

    Ryu, Hyejin; Lei, Hechang; Wang, Kefeng; Graf, D.; Bozin, Emil S.; Warren, J. B.; Petrovic, C.

    2013-03-01

    We report physical properties and ground state phase diagram of Kx(Fe,Ni)2-ySe2 single crystal alloy series. The ground state evolves from a heavy-Fermion-like metal KxNi2-ySe2 (I4/mmm) to a phase separated superconducting KxFe2-ySe2 (I4/m and I4/mmm space groups). Intermediate alloys show rich variety of ground states including semiconducting magnetic spin glass as Ni is replaced by Fe. We will address magnetic, thermodynamic, electronic and thermal transport properties and their connection to relevant structural parameters. 1Work at Brookhaven is supported by the U.S. DOE under Contract No. DE-AC02-98CH10886 and in part by the Center for Emergent Superconductivity, an Energy Frontier Research Center funded by the U.S. DOE, Office for Basic Energy Science (H. L. and C. P). Work at the National High Magnetic Field Laboratory is supported by the DOE NNSA DEFG52-10NA29659 (D.G.), by the NSF Cooperative Agreement No. DMR-0654118, and by the state of Florida.

  12. Microstructural change during (liquid phase sintering) of W-Ni-Fe alloy

    SciTech Connect

    Park, J.K.; Eun, K.Y. ); Kang, S.L

    1989-05-01

    The changes of bulk density and microstructures during heating and liquid phase sintering of 98W-1Ni-1Fe compacts prepared from 1 and 5 {mu}m W powders have been observed in order to characterize the densification behavior. The compact prepared from a fine (1 {mu}m) W powder begins to densify rapidly at about 1200{degrees}C in the solid state during heating, attaining about 95 pct density upon reaching the liquid phase sintering temperature of 1460{degrees}C. The compact prepared from a coarse (5 {mu}m) W powder begins to densify rapidly at about 1400{degrees}C in the solid state, attaining about 87 pct density upon reaching the liquid phase sintering temperature. Thus, the skeleton of grains is already formed prior to liquid formation. During the isothermal liquid phase sintering, substantial grain growth occurs, and the liquid flows into both open and closed pores, filling them sequentially from the regions with small cross-sections. The grains subsequently grow into the liquid pockets which have been formed at the pore sites. The sequential pore filling by first liquid thus is shown to be the dominant densification process during the liquid phase sintering of this alloy.

  13. Effects of Fe concentration on the ion-irradiation induced defect evolution and hardening in Ni-Fe solid solution alloys

    DOE PAGESBeta

    Jin, Ke; Guo, Wei; Lu, Chenyang; Ullah, Mohammad W.; Zhang, Yanwen; Weber, William J.; Wang, Lumin; Poplawsky, Jonathan D.; Bei, Hongbin

    2016-12-01

    Understanding alloying effects on the irradiation response of structural materials is pivotal in nuclear engineering. In order to systematically explore the effects of Fe concentration on the irradiation-induced defect evolution and hardening in face-centered cubic Ni-Fe binary solid solution alloys, single crystalline Ni-xFe (x = 0–60 at%) alloys have been grown and irradiated with 1.5 MeV Ni ions. The irradiations have been performed over a wide range of fluences from 3 × 1013 to 3 × 1016 cm-2 at room temperature. Ion channeling technique has shown reduced damage accumulation with increasing Fe concentration in the low fluence regime, which ismore » consistent to the results from molecular dynamic simulations. We did not observe any irradiation-induced compositional segregation in atom probe tomography within the detection limit, even in the samples irradiated with high fluence Ni ions. Transmission electron microscopy analyses have further demonstrated that the defect size significantly decreases with increasing Fe concentration, indicating a delay in defect evolution. Furthermore, irradiation induced hardening has been measured by nanoindentation tests. Ni and the Ni-Fe alloys have largely different initial hardness, but they all follow a similar trend for the increase of hardness as a function of irradiation fluence.« less

  14. The Influence of Cooling Rate During Crystallization on the Effective Partitioning Coefficient in High-Entropy Alloys from Al-Ti-Co-Ni-Fe System

    NASA Astrophysics Data System (ADS)

    Górecki, Kamil; Bala, Piotr; Cios, Grzegorz; Koziel, Tomasz; Stępień, Milena; Wieczerzak, Krzysztof

    2016-07-01

    An influence of two different cooling rates on the microstructure and dispersion of the components of high-entropy alloy from Al-Ti-Co-Ni-Fe system has been examined. For investigated alloys, the effective partitioning coefficient has been calculated. This factor indicates the degree of segregation of elements and allows for the specification of the differences between dendrites and interdendritic regions. The obtained results allow for the conclusion that the cooling rate substantially affect the growth of dendrites and the volume fraction of interdendritic regions as well as the partitioning of elements in the alloy. Furthermore, the obtained results made it possible to compare the influence of the cooling rate and the chemical composition on the dispersion of the alloying elements.

  15. Experimental Investigations on Pulsed Nd:YAG Laser Welding of C17300 Copper-Beryllium and 49Ni-Fe Soft Magnetic Alloys

    SciTech Connect

    Mousavi, S. A. A. Akbari; Ebrahimzadeh, H.

    2011-01-17

    Copper-beryllium and soft magnetic alloys must be joined in electrical and electro-mechanical applications. There is a high difference in melting temperatures of these alloys which cause to make the joining process very difficult. In addition, copper-beryllium alloys are of age hardenable alloys and precipitations can brittle the weld. 49Ni-Fe alloy is very hot crack sensitive. Moreover, these alloys have different heat transfer coefficients and reflection of laser beam in laser welding process. Therefore, the control of welding parameters on the formation of adequate weld puddle composition is very difficult. Laser welding is an advanced technique for joining of dissimilar materials since it can precisely control and adjust the welding parameters. In this study, a 100W Nd:YAG pulsed laser machine was used for joining 49Ni-Fe soft magnetic to C17300 copper-beryllium alloys. Welding of samples was carried out autogenously by changing the pulse duration, diameter of beam, welding speed, voltage and frequency. The spacing between samples was set to almost zero. The ample were butt welded. It was required to apply high voltage in this study due to high reflection coefficient of copper alloys. Metallography, SEM analysis, XRD and microhardness measurement was used for survey of results. The results show that the weld strength depends upon the chemical composition of the joints. To change the wells composition and heat input of the welds, it was attempted to deviate the laser focus away from the weld centerline. The best strength was achieved by deviation of the laser beam away about 0.1mm from the weld centerline. The result shows no intermetallic compounds if the laser beam is deviated away from the joint.

  16. Application of the radioisotope excited X-ray fluorescence technique in charge optimization during thermite smelting of Fe-Ni, Fe-cr, and Fe-Ti alloys

    SciTech Connect

    Sharma, I.G.; Joseph, D.; Lal, M.; Bose, D.K.

    1995-10-01

    A wide range of ferroalloys are used to facilitate the addition of different alloying elements to molten steel. High-carbon ferroalloys are produced on a tonnage basis by carbothermic smelting in an electric furnace, and an aluminothermic route is generally adopted for small scale production of low-carbon varieties. The physicochemical principles of carbothermy and aluminothermy have been well documented in the literature. However, limited technical data are reported on the production of individual ferroalloys of low-carbon varieties from their selected resources. The authors demonstrate her the application of an energy dispersive X-ray fluorescence (EDXRF) technique in meeting the analytical requirements of a thermite smelting campaign, carried out with the aim of preparing low-carbon-low-nitrogen Fe-Ni, Fe-Cr, and Fe-Ti alloys from indigenously available nickel bearing spent catalyst, mineral chromite, and ilmenite/rutile, respectively. They have chosen the EDXRF technique to meet the analytical requirements because of its capability to analyze samples of ore, minerals, a metal, and alloys in different forms, such as powder, sponge, as-smelted, or as-cast, to obtain rapid multielement analyses with ease. Rapid analyses of thermite feed and product by this technique have aided in the appropriate alterations of the charge constitutents to obtain optimum charge consumption.

  17. Comparison of high temperature, high frequency core loss and dynamic B-H loops of two 50 Ni-Fe crystalline alloys and an iron-based amorphous alloy

    NASA Technical Reports Server (NTRS)

    Wieserman, W. R.; Schwarze, G. E.; Niedra, J. M.

    1991-01-01

    The availability of experimental data that characterizes the performance of soft magnetic materials for the combined conditions of high temperature and high frequency is almost nonexistent. An experimental investigation was conducted over the temperature range of 23 to 300 C and frequency range of 1 to 50 kHz to determine the effects of temperature and frequency on the core loss and dynamic B-H loops of three different soft magnetic materials; and oriented grain 50Ni-50Fe alloy, a nonoriented grain 50Ni-Fe alloy, and an iron based amorphous material (Metglas 2605SC). A comparison of these materials shows that the nonoriented grain 50Ni-50Fe alloy tends to have either the lowest or next lowest core loss for all temperatures and frequencies investigated.

  18. Influence of the chemical composition of rapidly quenched amorphous alloys (Ni, Fe, Cr)-B-Si on its crystallization process

    NASA Astrophysics Data System (ADS)

    Elmanov, G.; Dzhumaev, P.; Ivanitskaya, E.; Skrytnyi, V.; Ruslanov, A.

    2016-04-01

    This paper presents results of research of the structure and phase transformations during the multistage crystallization of the metallic glasses with the compositions Ni71,5Cr6,8Fe2,7B11,9Si7,1 and Ni63,4Cr7,4Fe4,3Mn0,8B15,6Si8,5 labeled as AWS BNi-2 according to American Welding Society. Differential scanning calorimetry (DSC), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDX) were used as experimental research methods. The influence of the alloys chemical composition (boron, manganese and iron) on the temperatures and the exothermic heat effects of phase transformations, as well as on the phase composition of alloys at three stages of crystallization was analyzed. We present a thermodynamic explanation of the observed heat effects. It has been shown that manganese has the main influence on the phase transformations temperatures and heat effects in these two alloys. It is also assumed that at the final crystallization stage simultaneously with the formation of phases Ni3B and β1-Ni3Si should occur the nucleation of borides of CrB type with high Cr and low Si content.

  19. Mechanochemical processing of nanocrystalline Ti-6Al-4V alloy

    NASA Astrophysics Data System (ADS)

    Pirzada, M. D. S.; (Sam) Froes, F. H.; Patankar, S. N.

    2004-06-01

    Synthesis of nanocrystalline Ti-6Al-4V was explored using mechanochemical processing. The reaction mixture was comprised of CaH2, Mg powder, anhydrous AlCl3, anhydrous VCl3, and TiCl4. The milled powder (reaction product) primarily consisted of nanocrystalline alloy hydride having a composition (Ti-6Al-4V)H1.942, along with MgCl2 and CaCl2 as by-products. Aqueous solutions of nitric acid, sulfuric acid, and 1 pct sodium sulfite were found to be very effective in leaching of the chlorides from the milled powder. The (Ti-6Al-4V)H1.942 on dehydrogenation at 375°C resulted in nanocrystalline Ti-6Al-4V alloy powder.

  20. Magnetic anisotropy in Ni-Fe-Ga-Co ferromagnetic shape memory alloys in the single-variant state.

    PubMed

    Morito, H; Fujita, A; Oikawa, K; Fukamichi, K; Kainuma, R; Kanomata, T; Ishida, K

    2009-02-18

    The effects of the addition of Co on the magnetic anisotropy in Ni(55-x)Fe(18)Ga(27)Co(x) (x = 1-6) single-variant ferromagnetic shape memory alloys have been investigated. By the addition of Co from 1 to 6 at.%, the Curie temperature T(C) is increased from 318 to 405 K, keeping the martensitic transformation temperatures above room temperature. As a result, the value of the uniaxial magnetic anisotropy constant |K(u)| at 300 K increases with increasing x of the Co concentration and the martensite phase of Ni(49)Fe(18)Ga(27)Co(6) exhibits a relatively high value of |K(u)| = 1.15 × 10(5) J m(-3) at 300 K. With increasing Co concentration, on the other hand, the c axis changes from the magnetic easy axis to the hard axis at 4.2 K, that is, the sign of K(u) is reversed from positive to negative between 2 and 3 at.% Co. Furthermore, K(u) in Ni(53)Fe(18)Ga(27)Co(2) is positive below 100 K and negative above 100 K up to T(C), reducing the magnetic anisotropy around 200 K. From the present results, it is evident that the magnetic anisotropy of Ni(55-x)Fe(18)Ga(27)Co(x) (x = 1-6) single-variant ferromagnetic shape memory alloys is very sensitive to Co concentration and also temperature.

  1. Indentation creep of nanocrystalline Cu-TiC alloys prepared by mechanical alloying

    SciTech Connect

    Shen, B.L.; Itoi, T.; Yamasaki, T.; Ogino, Y.

    2000-04-01

    In recent years, nanocrystalline materials have attracted much attention in materials research because they behave differently from conventional materials. For example, the nanocrystalline materials exhibit enhanced mechanical properties, such as high strength and hardness. The present study was performed to investigate the indentation creep mechanism of nanocrystalline Cu-TiC alloys which were prepared by HIP (Hot Isostatic Press) processing of MA (Mechanical Alloying) powders and hot rolling afterwards. As these materials have high densities and high structural stability, the authors could investigate creep behavior at wide temperature ranges below 0.5Tm (Tm is the melting temperature of copper).

  2. Tensile Properties of Electrodeposited Nanocrystalline Ni-Cu Alloys

    NASA Astrophysics Data System (ADS)

    Dai, P. Q.; Zhang, C.; Wen, J. C.; Rao, H. C.; Wang, Q. T.

    2016-02-01

    Nanocrystalline Ni-Cu alloys with a Cu content of 6, 10, 19, and 32 wt.% were prepared by pulse electrodeposition. The microstructure and tensile properties of the nanocrystalline Ni-Cu alloys were characterized by x-ray diffraction, transmission electron microscopy, and tensile testing. The x-ray diffraction analysis indicates that the structure of the nanocrystalline Ni-Cu alloys is a face-centered cubic, single-phase solid solution with an average grain size of 18 to 24 nm, and that the average grain size decreased with increasing Cu content. The ultimate tensile strength (~1265 to 1640 MPa) and elongation to failure (~5.8 to 8.9%) of the Ni-Cu alloys increased with increasing Cu content. The increase in tensile strength results from the solid solution and fine-grain strengthening. Elemental Cu addition results in a decrease in stacking fault energy, an increase in work hardening rate, a delay in plasticity instability, and consequently, a higher plasticity.

  3. Extreme creep resistance in a microstructurally stable nanocrystalline alloy.

    PubMed

    Darling, K A; Rajagopalan, M; Komarasamy, M; Bhatia, M A; Hornbuckle, B C; Mishra, R S; Solanki, K N

    2016-01-01

    Nanocrystalline metals, with a mean grain size of less than 100 nanometres, have greater room-temperature strength than their coarse-grained equivalents, in part owing to a large reduction in grain size. However, this high strength generally comes with substantial losses in other mechanical properties, such as creep resistance, which limits their practical utility; for example, creep rates in nanocrystalline copper are about four orders of magnitude higher than those in typical coarse-grained copper. The degradation of creep resistance in nanocrystalline materials is in part due to an increase in the volume fraction of grain boundaries, which lack long-range crystalline order and lead to processes such as diffusional creep, sliding and rotation. Here we show that nanocrystalline copper-tantalum alloys possess an unprecedented combination of properties: high strength combined with extremely high-temperature creep resistance, while maintaining mechanical and thermal stability. Precursory work on this family of immiscible alloys has previously highlighted their thermo-mechanical stability and strength, which has motivated their study under more extreme conditions, such as creep. We find a steady-state creep rate of less than 10(-6) per second-six to eight orders of magnitude lower than most nanocrystalline metals-at various temperatures between 0.5 and 0.64 times the melting temperature of the matrix (1,356 kelvin) under an applied stress ranging from 0.85 per cent to 1.2 per cent of the shear modulus. The unusual combination of properties in our nanocrystalline alloy is achieved via a processing route that creates distinct nanoclusters of atoms that pin grain boundaries within the alloy. This pinning improves the kinetic stability of the grains by increasing the energy barrier for grain-boundary sliding and rotation and by inhibiting grain coarsening, under extremely long-term creep conditions. Our processing approach should enable the development of

  4. Extreme creep resistance in a microstructurally stable nanocrystalline alloy

    NASA Astrophysics Data System (ADS)

    Darling, K. A.; Rajagopalan, M.; Komarasamy, M.; Bhatia, M. A.; Hornbuckle, B. C.; Mishra, R. S.; Solanki, K. N.

    2016-09-01

    Nanocrystalline metals, with a mean grain size of less than 100 nanometres, have greater room-temperature strength than their coarse-grained equivalents, in part owing to a large reduction in grain size. However, this high strength generally comes with substantial losses in other mechanical properties, such as creep resistance, which limits their practical utility; for example, creep rates in nanocrystalline copper are about four orders of magnitude higher than those in typical coarse-grained copper. The degradation of creep resistance in nanocrystalline materials is in part due to an increase in the volume fraction of grain boundaries, which lack long-range crystalline order and lead to processes such as diffusional creep, sliding and rotation. Here we show that nanocrystalline copper-tantalum alloys possess an unprecedented combination of properties: high strength combined with extremely high-temperature creep resistance, while maintaining mechanical and thermal stability. Precursory work on this family of immiscible alloys has previously highlighted their thermo-mechanical stability and strength, which has motivated their study under more extreme conditions, such as creep. We find a steady-state creep rate of less than 10-6 per second—six to eight orders of magnitude lower than most nanocrystalline metals—at various temperatures between 0.5 and 0.64 times the melting temperature of the matrix (1,356 kelvin) under an applied stress ranging from 0.85 per cent to 1.2 per cent of the shear modulus. The unusual combination of properties in our nanocrystalline alloy is achieved via a processing route that creates distinct nanoclusters of atoms that pin grain boundaries within the alloy. This pinning improves the kinetic stability of the grains by increasing the energy barrier for grain-boundary sliding and rotation and by inhibiting grain coarsening, under extremely long-term creep conditions. Our processing approach should enable the development of

  5. Extreme creep resistance in a microstructurally stable nanocrystalline alloy.

    PubMed

    Darling, K A; Rajagopalan, M; Komarasamy, M; Bhatia, M A; Hornbuckle, B C; Mishra, R S; Solanki, K N

    2016-09-14

    Nanocrystalline metals, with a mean grain size of less than 100 nanometres, have greater room-temperature strength than their coarse-grained equivalents, in part owing to a large reduction in grain size. However, this high strength generally comes with substantial losses in other mechanical properties, such as creep resistance, which limits their practical utility; for example, creep rates in nanocrystalline copper are about four orders of magnitude higher than those in typical coarse-grained copper. The degradation of creep resistance in nanocrystalline materials is in part due to an increase in the volume fraction of grain boundaries, which lack long-range crystalline order and lead to processes such as diffusional creep, sliding and rotation. Here we show that nanocrystalline copper-tantalum alloys possess an unprecedented combination of properties: high strength combined with extremely high-temperature creep resistance, while maintaining mechanical and thermal stability. Precursory work on this family of immiscible alloys has previously highlighted their thermo-mechanical stability and strength, which has motivated their study under more extreme conditions, such as creep. We find a steady-state creep rate of less than 10(-6) per second-six to eight orders of magnitude lower than most nanocrystalline metals-at various temperatures between 0.5 and 0.64 times the melting temperature of the matrix (1,356 kelvin) under an applied stress ranging from 0.85 per cent to 1.2 per cent of the shear modulus. The unusual combination of properties in our nanocrystalline alloy is achieved via a processing route that creates distinct nanoclusters of atoms that pin grain boundaries within the alloy. This pinning improves the kinetic stability of the grains by increasing the energy barrier for grain-boundary sliding and rotation and by inhibiting grain coarsening, under extremely long-term creep conditions. Our processing approach should enable the development of

  6. Influence of hot isostatic pressing on the structure and properties of an innovative low-alloy high-strength aluminum cast alloy based on the Al-Zn-Mg-Cu-Ni-Fe system

    NASA Astrophysics Data System (ADS)

    Akopyan, T. K.; Padalko, A. G.; Belov, N. A.

    2015-11-01

    Hot isostatic pressing (HIP) is applied for treatment of castings of innovative low-ally high-strength aluminum alloy, nikalin ATs6N0.5Zh based on the Al-Zn-Mg-Cu-Ni-Fe system. The influence of HIP on the structure and properties of castings is studied by means of three regimes of barometric treatment with different temperatures of isometric holding: t 1 = 505 ± 2°C, p 1 = 100 MPa, τ1 = 3 h (HIP1); t 2 = 525 ± 2°C, p 2 = 100 MPa, τ2 = 3 h (HIP2); and t 3 = 545 ± 2°C, p 3 = 100 MPa, τ3 = 3 h (HIP3). It is established that high-temperature HIP leads to actually complete elimination of porosity and additional improvement of the morphology of second phases. Improved structure after HIP provides improvement properties, especially of plasticity. In particular, after heat treatment according of regime HIP2 + T4 (T4 is natural aging), the alloy plasticity is improved by about two times in comparison with the initial state (from ~6 to 12%). While applying regime HIP3 + T6 (T6 is artificial aging for reaching the maximum strength), the plasticity has improved by more than three times in comparison with the initial state, as after treatment according to regimes HIP1 + T6 and HIP2 + T6 (from ~1.2 to ~5.0%), which are characterized by a lower HIP temperature.

  7. Magnetic Properties of Grain Boundaries of Nanocrystalline Ni and of Ni Precipitates in Nanocrystalline NiCu Alloys

    NASA Astrophysics Data System (ADS)

    Wolf, H.; Guan, Z.; Li, X.; Wichert, Th.

    2001-11-01

    Perturbed γγ-angular correlation spectroscopy (PAC) was used to investigate nanocrystalline Ni and NiCu alloys, which are prepared by pulsed electrodeposition (PED). Using diffusion for doping nanocrystalline Ni with 111In four different ordered grain boundary structures are observed, which are characterized by unique electric field gradients. The incorporation of 111In on substitutional bulk sites of Ni is caused by moving grain boundaries below 1000 K and by volume diffusion above 1000 K. The nanocrystalline NiCu alloys prepared by PED are microscopically inhomogeneous as observed by PAC. In contrast, this inhomogeneity cannot be detected by X-ray diffraction. The influence of the temperature of the electrolyte, the current density during deposition, and the optional addition of saccharin to the electrolyte on the homogeneity of nanocrystalline NiCu alloys was investigated.

  8. The Thermal Stability of Nanocrystalline Au-Cu Alloys

    SciTech Connect

    Jankowski, A F; Saw, C K; Hayes, J P

    2006-02-15

    Grain refinement to the nanocrystalline scale is known to enhance physical properties as strength and surface hardness. For the case of Au-Cu alloys, development of the pulsed electroplating has led to the functional control of nanocrystalline grain size in the as-deposited condition. The thermal aging of Au-Cu electrodeposits is now investigated to assess the stability of the nanocrystalline grain structure and the difference between two diffusion mechanisms. The mobility of grain boundaries, dominant at low temperatures, leads to coarsening of grain size whereas at high temperature the process of bulk diffusion dominates. Although the kinetics of bulk diffusion are slow below 500 K at 10{sup -20} cm{sup 2} {center_dot} sec, the kinetics of grain boundary diffusion are faster at 10{sup -16} cm{sup 2} {center_dot} sec. The diffusivity values indicate that the grain boundaries of the as-deposited nanocrystalline Au-Cu are mobile and sensitive to low-temperature anneal treatments affecting the grain size, hence the strength of the material.

  9. Diffusion, phase equilibria and partitioning experiments in the Ni-Fe-Ru system

    NASA Technical Reports Server (NTRS)

    Blum, Joel D.; Wasserburg, G. J.; Hutcheon, I. D.; Beckett, J. R.; Stolper, E. M.

    1989-01-01

    Results are presented on thin-film diffusion experiments designed to investigate phase equilibria in systems containing high concentrations of Pt-group elements, such as Ni-Fe-Ru-rich systems containing Pt, at temperatures of 1273, 1073, and 873 K. The rate of Ru diffusion in Ni was determined as a function of temperature, and, in addition, the degree of Pt and Ir partitioning between phases in a Ni-Fe-Ru-rich system and of V between phases in a Ni-Fe-O-rich system at 873 were determined. It was found that Pt preferentially partitions into the (gamma)Ni-Fe phase, whereas Ir prefers the (epsilon)Ru-Fe phase. V partitions strongly into Fe oxides relative to (gamma)Ni-Fe. These results have direct application to the origin and thermal history of the alloys rich in Pt-group elements in meteorites.

  10. Optical Properties of ZnO-Alloyed Nanocrystalline Films

    DOE PAGESBeta

    Che, Hui; Huso, Jesse; Morrison, John L.; Thapa, Dinesh; Huso, Michelle; Yeh, Wei Jiang; Tarun, M. C.; McCluskey, M. D.; Bergman, Leah

    2012-01-01

    ZnO is emore » merging as one of the materials of choice for UV applications. It has a deep excitonic energy level and a direct bandgap of ~3.4 eV. Alloying ZnO with certain atomic constituents adds new optical and electronic functionalities to ZnO. This paper presents research on M g x Z n 1 − x O and Z n S 1 − x O x nanocrystalline flexible films, which enable tunable optical properties in the deep-UV and in the visible range. The ZnO and Mg 0 .3 Zn 0 .7 O films were found to have bandgaps at 3.35 and 4.02 eV, respectively. The photoluminescence of the Mg 0 .3 Zn 0 .7 O exhibited a bandedge emission at 3.95 eV, and at lower energy 3.38 eV due to the limited solubility inherent to these alloys. ZnS 0 .76 O 0 .24 and ZnS 0 .16 O 0 .84 were found to have bandgaps at 3.21 and 2.65 eV, respectively. The effect of nitrogen doping on ZnS 0 .16 O 0 .84 is discussed in terms of the highly lattice mismatched nature of these alloys and the resulting valence-band modification.« less

  11. Simulation of grain size effects in nanocrystalline shape memory alloys

    NASA Astrophysics Data System (ADS)

    Ahluwalia, Rajeev; Quek, Siu Sin; Wu, David T.

    2015-06-01

    Recently, it has been demonstrated that martensitic transformation in nanocrystalline shape memory alloys can be suppressed for small grain sizes. Motivated by these results, we study the grain size dependence of martensitic transformations and stress-strain response of nanocrystalline shape memory alloys within the framework of the Ginzburg-Landau (GL) theory. A GL model for a square to rectangle transformation in polycrystals is extended to account for grain boundary effects. We propose that an inhibition of the transformation in grain boundary regions can occur, if the grain boundary energy of the martensite is higher than that of the austenite phase. We show that this inhibition of transformation in grain boundary regions has a strong influence on domain patterns inside grains. Although the transformation is inhibited only at the grain boundaries, it leads to a suppression of the transformation even inside the grains as grain size is decreased. In fact, below a critical grain size, the transformation can be completely suppressed. We explain these results in terms of the extra strain gradient cost associated with grain boundaries, when the transformation is inhibited at grain boundaries. On the other hand, no significant size effects are observed when transformation is not inhibited at grain boundaries. We also study the grain size dependence of the stress strain curve. It is found that when the transformation is inhibited at grain boundaries, a significant reduction in the hysteresis associated with stress-strain curves during the loading-unloading cycles is observed. The hysteresis for this situation reduces even further as the grain size is reduced, which is consistent with recent experiments. The simulations also demonstrate that the mechanical behavior is influenced by inter-granular interactions and the local microstructural neighbourhood of a grain has a stronger influence than the orientation of the grain itself.

  12. Elastic moduli of nanocrystalline binary Al alloys with Fe, Co, Ti, Mg and Pb alloying elements

    NASA Astrophysics Data System (ADS)

    Babicheva, Rita I.; Bachurin, Dmitry V.; Dmitriev, Sergey V.; Zhang, Ying; Kok, Shaw Wei; Bai, Lichun; Zhou, Kun

    2016-05-01

    The paper studies the elastic moduli of nanocrystalline (NC) Al and NC binary Al-X alloys (X is Fe, Co, Ti, Mg or Pb) by using molecular dynamics simulations. X atoms in the alloys are either segregated to grain boundaries (GBs) or distributed randomly as in disordered solid solution. At 0 K, the rigidity of the alloys increases with decrease in atomic radii of the alloying elements. An addition of Fe, Co or Ti to the NC Al leads to increase in the Young's E and shear μ moduli, while an alloying with Pb decreases them. The elastic moduli of the alloys depend on a distribution of the alloying elements. The alloys with the random distribution of Fe or Ti demonstrate larger E and μ than those for the corresponding alloys with GB segregations, while the rigidity of the Al-Co alloy is higher for the case of the GB segregations. The moduli E and μ for polycrystalline aggregates of Al and Al-X alloys with randomly distributed X atoms are estimated based on the elastic constants of corresponding single-crystals according to the Voigt-Reuss-Hill approximation, which neglects the contribution of GBs to the rigidity. The results show that GBs in NC materials noticeably reduce their rigidity. Furthermore, the temperature dependence of μ for the NC Al-X alloys is analyzed. Only the Al-Co alloy with GB segregations shows the decrease in μ to the lowest extent in the temperature range of 0-600 K in comparison with the NC pure Al.

  13. Microstructure and aging behavior of conventional and nanocrystalline aluminum-copper-magnesium alloys with scandium additions

    NASA Astrophysics Data System (ADS)

    Zuniga, Alejandro

    The influence of small amounts of scandium (0.15 and 0.3 wt.%) on the microstructure, aging behavior and mechanical properties of 2618 (Al-Cu-Mg-Fe-Ni) and C416 (Al-Cu-Mg-Ag-Mn) alloys was studied. It was observed the overall precipitation sequence and the general morphology of the aging curve were not affected by the addition of small amounts of Sc. It was also observed that a separate population of small Al3Sc particles improved the aging response and mechanical properties of low-Cu, low-Sc Al-Cu-Mg alloys, while the formation of Al5-8Cu7-4Sc particles resulted in a decrease of the mechanical properties in high-Cu Sc-containing alloys. The Sc-modified with the best aging response (2618 + 0.15 % Sc) was cryomilled in order to produce Al-Cu-Mg-Fe-Ni-Sc nanocrystalline powders. Bulk nanocrystalline samples were consolidated from the cryomilled powder using three different techniques: hot isostatic pressing and extrusion, spark plasma sintering, cold spraying. The influence of consolidation technique on the microstructure, aging behavior and mechanical properties was analyzed. The extruded and spark plasma sintered Al-Cu-Mg-Fe-Ni-Sc nanocrystalline samples presented a bimodal grain structure consisting of coarse-grained regions located at the inter-particle region, and nanocrystalline regions at the particle interiors. The aging behavior of the nanocrystalline Al-Cu-Mg-Fe-Ni-Sc alloy was characterized by softening instead of hardening. This behavior was rationalized on the basis of changes in the precipitation processes that occur in the nanocrystalline state. On the other hand, the cold spray process promoted the formation of truly nanocrystalline coatings. The mechanisms influencing the coating formation of conventional and nanocrystalline Al-Cu-Mg-Fe-Ni-Sc samples were analyzed.

  14. Nanocrystalline films of soft magnetic iron-based alloys

    NASA Astrophysics Data System (ADS)

    Sheftel', E. N.; Bannykh, O. A.

    2006-10-01

    The physicochemical and structural aspects of designing soft magnetic alloys Fe- MX (where M is a Group III V metal of the periodic table and X = C, N, O) in the form of nanocrystalline films precipitation-hardened by refractory interstitial phases are discussed and developed. The results of studying the structure and magnetic properties of Fe78Zr10N12 films are reported. The films in the amorphous state are produced by reactive magnetron sputtering. Upon annealing at 300 600°C, the amorphous films crystallize to form mainly a bcc α-Fe-based phase and the fcc ZrN phase. The grain size of the bcc phase is shown to increase from ˜3 nm to ˜30 nm as the annealing temperature increases; the grain size of the fcc phase does not exceed 2 3 nm. Films annealed at 400°C exhibit a record level of magnetic properties: H c = 5 6 A/m and B s = 1.7 1.8 T. The experimental results obtained confirm the validity of our scientific approach.

  15. Abiotic ammonium formation in the presence of Ni-Fe metals and alloys and its implications for the Hadean nitrogen cycle

    PubMed Central

    Smirnov, Alexander; Hausner, Douglas; Laffers, Richard; Strongin, Daniel R; Schoonen, Martin AA

    2008-01-01

    Experiments with dinitrogen-, nitrite-, nitrate-containing solutions were conducted without headspace in Ti reactors (200°C), borosilicate septum bottles (70°C) and HDPE tubes (22°C) in the presence of Fe and Ni metal, awaruite (Ni80Fe20) and tetrataenite (Ni50Fe50). In general, metals used in this investigation were more reactive than alloys toward all investigated nitrogen species. Nitrite and nitrate were converted to ammonium more rapidly than dinitrogen, and the reduction process had a strong temperature dependence. We concluded from our experimental observations that Hadean submarine hydrothermal systems could have supplied significant quantities of ammonium for reactions that are generally associated with prebiotic synthesis, especially in localized environments. Several natural meteorites (octahedrites) were found to contain up to 22 ppm Ntot. While the oxidation state of N in the octahedrites was not determined, XPS analysis of metals and alloys used in the study shows that N is likely present as nitride (N3-). This observation may have implications toward the Hadean environment, since, terrestrial (e.g., oceanic) ammonium production may have been supplemented by reduced nitrogen delivered by metal-rich meteorites. This notion is based on the fact that nitrogen dissolves into metallic melts. PMID:18489746

  16. Giant and reversible room-temperature elastocaloric effect in a single-crystalline Ni-Fe-Ga magnetic shape memory alloy.

    PubMed

    Li, Yang; Zhao, Dewei; Liu, Jian

    2016-01-01

    Good mechanical properties and large adiabatic temperature change render Heusler-type Ni2FeGa-based magnetic shape memory alloys as a promising candidate material for solid-state mechanical cooling application at ambient conditions. Superelastic behavior and associated elastocaloric effect strongly reply on deformation conditions (e.g. applied strain rate and strain level) of stress-induced martensitic transformations. With the aim of developing high-performance elastic cooling materials, in this work, we have carried out a systematic study on a Ni54Fe19Ga27 [420]-oriented single crystal by exploring the interaction between dynamic deformation parameters and thermal response. A giant and reversible adiabatic temperature change of ±7.5 K triggered by a low stress of 30 MPa was achieved. Such a high specific cooling performance thus offers the great advantage for the small scale solid-state mechanical cooling applications. Besides, a significant temporary residual strain effect has been observed at high strain rate, which is unfavorable for reversible elastocaloric effect but can be overcome by reducing stress hysteresis, and/or by elevating initial environmental temperature. The established criterion for the desirable reversible elastocaloric properties goes beyond the present system, and can be applicable for other shape memory alloys used for elastic cooling techniques. PMID:27138030

  17. Giant and reversible room-temperature elastocaloric effect in a single-crystalline Ni-Fe-Ga magnetic shape memory alloy

    PubMed Central

    Li, Yang; Zhao, Dewei; Liu, Jian

    2016-01-01

    Good mechanical properties and large adiabatic temperature change render Heusler-type Ni2FeGa-based magnetic shape memory alloys as a promising candidate material for solid-state mechanical cooling application at ambient conditions. Superelastic behavior and associated elastocaloric effect strongly reply on deformation conditions (e.g. applied strain rate and strain level) of stress-induced martensitic transformations. With the aim of developing high-performance elastic cooling materials, in this work, we have carried out a systematic study on a Ni54Fe19Ga27 [420]-oriented single crystal by exploring the interaction between dynamic deformation parameters and thermal response. A giant and reversible adiabatic temperature change of ±7.5 K triggered by a low stress of 30 MPa was achieved. Such a high specific cooling performance thus offers the great advantage for the small scale solid-state mechanical cooling applications. Besides, a significant temporary residual strain effect has been observed at high strain rate, which is unfavorable for reversible elastocaloric effect but can be overcome by reducing stress hysteresis, and/or by elevating initial environmental temperature. The established criterion for the desirable reversible elastocaloric properties goes beyond the present system, and can be applicable for other shape memory alloys used for elastic cooling techniques. PMID:27138030

  18. Giant and reversible room-temperature elastocaloric effect in a single-crystalline Ni-Fe-Ga magnetic shape memory alloy.

    PubMed

    Li, Yang; Zhao, Dewei; Liu, Jian

    2016-05-03

    Good mechanical properties and large adiabatic temperature change render Heusler-type Ni2FeGa-based magnetic shape memory alloys as a promising candidate material for solid-state mechanical cooling application at ambient conditions. Superelastic behavior and associated elastocaloric effect strongly reply on deformation conditions (e.g. applied strain rate and strain level) of stress-induced martensitic transformations. With the aim of developing high-performance elastic cooling materials, in this work, we have carried out a systematic study on a Ni54Fe19Ga27 [420]-oriented single crystal by exploring the interaction between dynamic deformation parameters and thermal response. A giant and reversible adiabatic temperature change of ±7.5 K triggered by a low stress of 30 MPa was achieved. Such a high specific cooling performance thus offers the great advantage for the small scale solid-state mechanical cooling applications. Besides, a significant temporary residual strain effect has been observed at high strain rate, which is unfavorable for reversible elastocaloric effect but can be overcome by reducing stress hysteresis, and/or by elevating initial environmental temperature. The established criterion for the desirable reversible elastocaloric properties goes beyond the present system, and can be applicable for other shape memory alloys used for elastic cooling techniques.

  19. Giant and reversible room-temperature elastocaloric effect in a single-crystalline Ni-Fe-Ga magnetic shape memory alloy

    NASA Astrophysics Data System (ADS)

    Li, Yang; Zhao, Dewei; Liu, Jian

    2016-05-01

    Good mechanical properties and large adiabatic temperature change render Heusler-type Ni2FeGa-based magnetic shape memory alloys as a promising candidate material for solid-state mechanical cooling application at ambient conditions. Superelastic behavior and associated elastocaloric effect strongly reply on deformation conditions (e.g. applied strain rate and strain level) of stress-induced martensitic transformations. With the aim of developing high-performance elastic cooling materials, in this work, we have carried out a systematic study on a Ni54Fe19Ga27 [420]-oriented single crystal by exploring the interaction between dynamic deformation parameters and thermal response. A giant and reversible adiabatic temperature change of ±7.5 K triggered by a low stress of 30 MPa was achieved. Such a high specific cooling performance thus offers the great advantage for the small scale solid-state mechanical cooling applications. Besides, a significant temporary residual strain effect has been observed at high strain rate, which is unfavorable for reversible elastocaloric effect but can be overcome by reducing stress hysteresis, and/or by elevating initial environmental temperature. The established criterion for the desirable reversible elastocaloric properties goes beyond the present system, and can be applicable for other shape memory alloys used for elastic cooling techniques.

  20. Microstructural evolution of nanocrystalline Fe–Zr alloys upon annealing treatment

    SciTech Connect

    Shi, X.H.; Chen, Y.Z.; Ma, X.Y.; Wang, H.T.; Liu, F.

    2015-05-15

    Nanocrystalline Fe–Zr alloys exhibit an extraordinary thermal stability at elevated temperatures, which enables their potential applications in various fields. However, there remain concerns regarding the controlling stabilization mechanisms responsible for their thermal stability. In this work, two nanocrystalline Fe–Zr alloys containing 1 at.% Zr and 5 at.% Zr were annealed at various temperatures (T{sub ann}) up to 900 °C. Microstructural evolution of the alloys upon annealing was investigated by means of an X-ray diffractometer equipped with a 2-dimensional detector and transmission electron microscopy. Below 600 °C, microstructures of the two alloys consist of single nanocrystalline ferrite whose grain size is rather stable upon annealing treatments. Above 600 °C, accompanying the precipitation of Fe{sub 3}Zr phase, an apparent grain coarsening of ferrite is observed, whereas the thermal stability of the alloys is still considerably higher than that of nanocrystalline pure Fe. Based on the experimental results, it was claimed that stabilization of the nanocrystalline Fe–Zr alloys should not be totally ascribed to the thermodynamic stabilization mechanism due to the reduction in grain boundary energy as suggested in earlier investigations [K.A. Darling et al., Scr. Mater. 59 (2008) 530 and K.A. Darling et al., Mater. Sci. Eng. A527 (2010) 3572]; when T{sub ann} is higher than 600 °C, along with the precipitation of Fe{sub 3}Zr, the effect of thermodynamic stabilization is weakened, the kinetic effect arising from Zener pinning of Fe{sub 3}Zr precipitates turns to be an important mechanism contributing to the stabilization of the nanoscale grain size. - Highlights: • We show clear evidence of precipitation of Fe{sub 3}Zr phase above 600 °C. • Stabilization of nanostructure is not solely controlled by thermodynamic mechanism. • Above 600 °C, Zener pinning plays an important role in stabilizing nanostructure.

  1. Cu-Ni-Fe anodes having improved microstructure

    DOEpatents

    Bergsma, S. Craig; Brown, Craig W.

    2004-04-20

    A method of producing aluminum in a low temperature electrolytic cell containing alumina dissolved in an electrolyte. The method comprises the steps of providing a molten electrolyte having alumina dissolved therein in an electrolytic cell containing the electrolyte. A non-consumable anode and cathode is disposed in the electrolyte, the anode comprised of Cu--Ni--Fe alloys having single metallurgical phase. Electric current is passed from the anode, through the electrolyte to the cathode thereby depositing aluminum on the cathode, and molten aluminum is collected from the cathode.

  2. Deformation behavior and microstructural evolution of nanocrystalline aluminum alloys and composites

    NASA Astrophysics Data System (ADS)

    Ahn, Byungmin

    Nanocrystalline or ultrafine-grained Al alloys are often produced by severe plastic deformation methods and exhibit remarkably enhanced strength and hardness compared to conventional coarse-grained materials, resulting in great potential for structural applications. To achieve nanocrystalline structure, grains were refined by cryomilling (mechanical milling at cryogenic temperature) pre-alloyed powders. Cryomilling provides capability for rapid grain refinement and synthesis of commercial quantities (30-40 kg). The cryomilled powder was primarily consolidated by hot or cold isostatic pressing in general. Secondary consolidation was achieved by extrusion or forging. Alternatively, quasi-isostatic forging was applied either as an initial consolidation or as a further deformation step. To improve insufficient ductility and toughness of nanocrystalline materials, an intelligent design with microstructural modification was introduced by generation of multiple size scales. A bimodal grain structure consisting of nanocrystalline grains and inclusions of coarse-grained material was produced by consolidation of blended powders. The resulting materials exhibited enhanced ductility compared to 100% nanocrystalline materials, with only moderate decreases in strength. A similar process was used to produce hybrid trimodal microstructures comprised of regions of nanocrystalline and coarse grains, as well as hard ceramic particles, providing super-high compressive strength. For cryomilled nanocrystalline Al alloys, effects of degassing temperature were investigated in terms of microstructural evolution. Higher degassing temperatures resulted in higher density and lower hydrogen content, which can reduce loss of toughness in consolidated materials. Different consolidation methods were compared with regard to the relation between the microstructures and mechanical properties. Quasi-isostatic forging led to greater and more isotropic fracture toughness, compared with other processing

  3. Structural, thermal and magnetic investigations on immiscible Ag-Co nanocrystalline alloy with addition of Mn

    NASA Astrophysics Data System (ADS)

    Mondal, B. N.; Chabri, S.; Sardar, G.; Nath, D. N.; Chattopadhyay, P. P.

    2016-08-01

    50Ag-50Co (at%) and 40Ag-40Co-20Mn (at%) alloys prepared by ball milling up to 50 h and subsequent isothermal annealing at the temperature range of 350-650 °C for 1 h has been investigated systematically. Mn promotes early formation of the nanostructures and solid solutions of the alloys by ball milling. In contrast, annealing at 350 °C of Ag-Co alloy resulted the dissolution of hcp Co. Annealing above 350 °C decomposes the metastable Ag-Co alloy into the polycrystalline and segregated Ag and fcc Co. Enthalpy of mixing of both the alloy has increased with increase in milling time. Both the nanocrystalline alloys prepared by ball milling and annealing have been revealed the ferromagnetic behavior. The most significant improvement of magnetic properties is yielded in as-milled Ag-Co-Mn alloy obtained after annealing at 550 °C for 1 h.

  4. "Bulk" Nanocrystalline Metals: Review of the Current State of the Art and Future Opportunities for Copper and Copper Alloys

    NASA Astrophysics Data System (ADS)

    Tschopp, M. A.; Murdoch, H. A.; Kecskes, L. J.; Darling, K. A.

    2014-06-01

    It is a new beginning for innovative fundamental and applied science in nanocrystalline materials. Many of the processing and consolidation challenges that have haunted nanocrystalline materials are now more fully understood, opening the doors for bulk nanocrystalline materials and parts to be produced. While challenges remain, recent advances in experimental, computational, and theoretical capability have allowed for bulk specimens that have heretofore been pursued only on a limited basis. This article discusses the methodology for synthesis and consolidation of bulk nanocrystalline materials using mechanical alloying, the alloy development and synthesis process for stabilizing these materials at elevated temperatures, and the physical and mechanical properties of nanocrystalline materials with a focus throughout on nanocrystalline copper and a nanocrystalline Cu-Ta system, consolidated via equal channel angular extrusion, with properties rivaling that of nanocrystalline pure Ta. Moreover, modeling and simulation approaches as well as experimental results for grain growth, grain boundary processes, and deformation mechanisms in nanocrystalline copper are briefly reviewed and discussed. Integrating experiments and computational materials science for synthesizing bulk nanocrystalline materials can bring about the next generation of ultrahigh strength materials for defense and energy applications.

  5. Solid-state synthesis and phase transformations in Ni/Fe films: Structural and magnetic studies

    NASA Astrophysics Data System (ADS)

    Myagkov, V. G.; Zhigalov, V. C.; Bykova, L. E.; Bondarenko, G. N.

    2006-10-01

    We have used X-ray diffraction, volume magnetocrystalline anisotropy constant and resistance measurements to study solid-state synthesis in Ni(0 0 1)/Fe(0 0 1), Ni/Fe(0 0 1) and Ni/Fe thin films with the atomic ratio between Fe and Ni of 1:1 (1Fe:1Ni), and 3:1 (3Fe:1Ni). We have found that the formation of Ni 3Fe and NiFe phases in the 1Fe:1Ni films takes place at temperatures ˜620 and ˜720 K, correspondingly. In the case of the 3Fe:1Ni films the solid-state synthesis starts with Ni 3Fe and NiFe phase formation at the same temperatures as for the 1Fe:1Ni films. The increasing of annealing temperature above 820 K leads to the nucleation of a paramagnetic γpar phase at the FeNi/Fe interface. The final products of solid-state synthesis in the Ni(0 0 1)/Fe(0 0 1) thin films are crystallites which consist of the epitaxially intergrown NiFe and γpar phases according to the [1 0 0](0 0 1)NiFe||[1 0 0](0 0 1) γpar orientation relationship. The crystalline perfection and epitaxial growth of the (NiFe+ γpar) crystallites on the MgO(0 0 1) surface allow to distinguish (0 0 2) γpar and (0 0 2)NiFe X-ray peaks (the cell parameters are: a( γpar)=0.3600±0.0005 nm and a(NiFe)=0.3578±0.0005 nm, correspondingly). At low temperatures the paramagnetic γpar phase undergoes the martensite γ→α' phase transition which can be hindered by thermal and epitaxial strains and epitaxial clamping with a MgO substrate. On the basis of the studies of the thin-film solid-state synthesis we predict the existence of two novel structural phase transformations at the temperatures of about 720 and 820 K for alloys of the invar region of the Fe-Ni system.

  6. [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

  7. [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

  8. CORROSION OF AMORPHOUS AND NANOCRYSTALLINE Fe-BASED ALLOYS IN NaCl AND H2SO4 SOLUTIONS

    NASA Astrophysics Data System (ADS)

    Li, Xiang; Lu, Wei; Wang, Yuxin; Yan, Biao; Pan, Deng

    2013-07-01

    Corrosion resistance of nanocrystalline Fe73.5Si13.5B9Nb3Cu1 alloy was investigated and compared to its amorphous counterpart. Low-temperature crystallization occurred during the annealing of amorphous tapes was used to obtain a nanocrystalline structure. The influence of annealing condition on the structure and corrosion resistance of the alloy in NaCl and H2SO4 solutions was investigated. Based on the testing results, it was found that nanocrystalline tapes have higher corrosion resistance than amorphous counterpart and H2SO4 can promote the occurrence of corrosion compared with NaCl.

  9. Microstructure and magnetic properties of soft magnetic powder cores of amorphous and nanocrystalline alloys

    NASA Astrophysics Data System (ADS)

    Liu, Yapi; Yi, Yide; Shao, Wei; Shao, Yanfang

    2013-03-01

    With the development of modern ferromagnetic technology, soft magnetic powder cores (MPCs) of amorphous and nanocrystalline alloys have been intensively studied for their excellent soft magnetic properties such as high flux density, low coercivity and reduced core loss due to amorphous state and nanocrystalline grains of 10-20 nm dispersed in a residual amorphous matrix. In this paper, the microstructures and soft magnetic properties, i.e., maximum magnetic induction Bm, effective permeability μe, DC-bias properties and volume power losses PCV of MPCs made from amorphous powder of gas atomization and nanocrystalline powder of pulverized melt-spun ribbon were investigated and also compared on the basis of the same level of μe. It is found that μe of both kinds of MPC keeps unchanged up to 1 MHz. The amorphous MPC has lower PCV at lower frequency range, while the nanocrystalline MPC has lower PCV at high frequency range instead. Also, the nanocrystalline MPC has better DC-bias property. Moreover, the DC magnetic properties and the changes of PCV of both MPCs with frequency and flux density are also studied. Furthermore, the electromagnetic characteristics, the microstructures and the mechanisms accounting for these phenomena of both MPCs are also discussed.

  10. Plasticity of nanocrystalline alloys with chemical order: on the strength and ductility of nanocrystalline Ni–Fe

    PubMed Central

    Albe, Karsten

    2013-01-01

    Summary Plastic deformation and alloying of nanocrystalline Ni–Fe is studied by means of atomic scale computer simulations. By using a combination of Monte-Carlo and molecular dynamics methods we find that solutes have an ordering tendency even if grain sizes are in the nanometer regime, where the phase field of the ordered state is widened as compared to larger grain sizes. Tensile testing of disordered structures with various elemental distributions and the simultaneous analysis of intragranular defects reveal that solid solution strengthening is absent for the studied grain sizes. The composition and relaxation state of the grain boundary control the strength of the material, which is also found for ordered structures (L12), where dislocation activity is suppressed. PMID:24205450

  11. Electrodeposition of nanocrystalline Zn-Ni alloy from alkaline glycinate bath containing saccharin as additive

    NASA Astrophysics Data System (ADS)

    Mosavat, S. H.; Bahrololoom, M. E.; Shariat, M. H.

    2011-08-01

    Nanocrystalline Zn-Ni (crystallite sizes 13-68 nm) alloy coatings were produced from an alkaline glycinate bath containing saccharin as additive. X-ray diffraction (XRD) was used to determine the phase composition and average crystallite size of nanocrystalline Zn-Ni alloy coatings. The average grain size of a deposit was also studied by transmission electron microscopy (TEM). The effects of saccharin concentration and current density on the crystallite size and surface roughness of the coatings were studied. Crystallite size and average surface roughness were diminished as a result of increasing saccharin concentration. Scanning electron microscopy (SEM) examination showed that coatings had a colony-like morphology and the colony size was increased with increasing current density. Microhardness testing was carried out in order to determine the degree of dependence of this mechanical property on the crystallite size. It was found that microhardness did not depend on crystallite size (Hall-Petch).

  12. Novel synthesis of Ni-ferrite (NiFe{sub 2}O{sub 4}) electrode material for supercapacitor applications

    SciTech Connect

    Venkatachalam, V.; Jayavel, R.

    2015-06-24

    Novel nanocrystalline NiFe{sub 2}O{sub 4} has been synthesized through combustion route using citric acid as a fuel. Phase of the synthesized material was analyzed using powder X-ray diffraction. The XRD study revealed the formation of spinel phase cubic NiFe{sub 2}O{sub 4} with high crystallinity. The average crystallite size of NiFe{sub 2}O{sub 4} nanomaterial was calculated from scherrer equation. The electrochemical properties were realized by cyclic voltammetry, chronopotentiometry and electrochemical impedance spectroscopy. The electrode material shows a maximum specific capacitance of 454 F/g with pseudocapacitive behavior. High capacitance retention of electrode material over 1000 continuous charging-discharging cycles suggests its excellent electrochemical stability. The results revealed that the nickel ferrite electrode is a potential candidate for energy storage applications in supercapacitor.

  13. Novel synthesis of Ni-ferrite (NiFe2O4) electrode material for supercapacitor applications

    NASA Astrophysics Data System (ADS)

    Venkatachalam, V.; Jayavel, R.

    2015-06-01

    Novel nanocrystalline NiFe2O4 has been synthesized through combustion route using citric acid as a fuel. Phase of the synthesized material was analyzed using powder X-ray diffraction. The XRD study revealed the formation of spinel phase cubic NiFe2O4 with high crystallinity. The average crystallite size of NiFe2O4 nanomaterial was calculated from scherrer equation. The electrochemical properties were realized by cyclic voltammetry, chronopotentiometry and electrochemical impedance spectroscopy. The electrode material shows a maximum specific capacitance of 454 F/g with pseudocapacitive behavior. High capacitance retention of electrode material over 1000 continuous charging-discharging cycles suggests its excellent electrochemical stability. The results revealed that the nickel ferrite electrode is a potential candidate for energy storage applications in supercapacitor.

  14. Magnetic induction heating of FeCr nanocrystalline alloys

    NASA Astrophysics Data System (ADS)

    Gómez-Polo, C.; Larumbe, S.; Pérez-Landazábal, J. I.; Pastor, J. M.; Olivera, J.; Soto-Armañanzas, J.

    2012-06-01

    In this work the thermal effects of magnetic induction heating in (FeCr)73.5Si13.5Cu1B9Nb3 amorphous and nanocrystalline wires were analyzed. A single piece of wire was immersed in a glass capillary filled with water and subjected to an ac magnetic field (frequency, 320 kHz). The initial temperature rise enabled the determination of the effective Specific Absorption Rate (SAR). Maximum SAR values are achieved for those samples displaying high magnetic susceptibility, where the eddy current losses dominate the induction heating behavior. Moreover, the amorphous sample with Curie temperature around room temperature displays characteristic features of self-regulated hyperthermia.

  15. Thermal Stability Comparison of Nanocrystalline Fe-Based Binary Alloy Pairs

    NASA Astrophysics Data System (ADS)

    Clark, B. G.; Hattar, K.; Marshall, M. T.; Chookajorn, T.; Boyce, B. L.; Schuh, C. A.

    2016-06-01

    The widely recognized property improvements of nanocrystalline (NC) materials have generated significant interest; yet, they have been difficult to realize in engineering applications due to the propensity for grain growth in these interface-dominated systems. Although traditional pathways to thermal stabilization can slow the mobility of grain boundaries, recent theories suggest that solute segregation in NC alloys can reduce the grain boundary energy such that thermodynamic stabilization is achieved. Following the predictions of Murdoch et al., here we compare for the first time the thermal stability of a predicted NC stable alloy (Fe-10 at.% Mg) with a predicted non-NC stable alloy (Fe-10 at.% Cu) using the same processing and characterization methodologies. Results show improved thermal stability of the Fe-Mg alloy in comparison with the Fe-Cu, and thermally-evolved microstructures that are consistent with those predicted by Monte Carlo simulations.

  16. Thermal stability comparison of nanocrystalline Fe-based binary alloy pairs

    DOE PAGESBeta

    Clark, Blythe G.; Hattar, Khalid Mikhiel; Marshall, Michael Thomas; Chookajorn, Tonghai; Boyce, Brad L.; Schuh, Christopher A.

    2016-02-01

    Here, the widely recognized property improvements of nanocrystalline (NC) materials have generated significant interest, yet have been difficult to realize in engineering applications due to the propensity for grain growth in these interface-dense systems. While traditional pathways to thermal stabilization can slow the mobility of grain boundaries, recent theories suggest that solute segregation in NC alloy can reduce the grain boundary energy such that thermodynamic stabilization is achieved. Following the predictions of Murdock et al., here we compare for the first time the thermal stability of a predicted NC stable alloy (Fe-10at.% Mg) with a predicted non-NC stable alloy (Fe-10at.%more » Cu) using the same processing and characterization methodologies. Results indicate improved thermal stability of the Fe-Mg alloy in comparison to the Fe-Cu, and observed microstructures are consistent with those predicted by Monte Carlo simulations.« less

  17. Formation and Stability of Equiatomic and Nonequiatomic Nanocrystalline CuNiCoZnAlTi High-Entropy Alloys by Mechanical Alloying

    NASA Astrophysics Data System (ADS)

    Varalakshmi, S.; Kamaraj, M.; Murty, B. S.

    2010-10-01

    Nanocrystalline equiatomic high-entropy alloys (HEAs) have been synthesized by mechanical alloying in the Cu-Ni-Co-Zn-Al-Ti system from the binary CuNi alloy to the hexanary CuNiCoZnAlTi alloy. An attempt also has been made to find the influence of nonequiatomic compositions on the HEA formation by varying the Cu content up to 50 at. pct (Cu x NiCoZnAlTi; x = 0, 8.33, 33.33, 49.98 at. pct). The phase formation and stability of mechanically alloyed powder at an elevated temperature (1073 K [800 °C] for 1 hour) were studied. The nanocrystalline equiatomic Cu-Ni-Co-Zn-Al-Ti alloys have a face-centered cubic (fcc) structure up to quinary compositions and have a body-centered cubic (bcc) structure in a hexanary alloy. In nonequiatomic alloys, bcc is the dominating phase in the alloys containing 0 and 8.33 at. pct of Cu, and the fcc phase was observed in alloys with 33.33 and 49.98 at. pct of Cu. The Vicker’s bulk hardness and compressive strength of the equiatomic nanocrystalline hexanary CuNiCoZnAlTi HEA after hot isostatic pressing is 8.79 GPa, and the compressive strength is 2.76 GPa. The hardness of these HEAs is higher than most commercial hard facing alloys ( e.g., Stellite, which is 4.94 GPa).

  18. Microstructure and physical properties of laser Zn modified amorphous-nanocrystalline coating on a titanium alloy

    NASA Astrophysics Data System (ADS)

    Li, Jia-Ning; Gong, Shui-Li; Shi, Yi-Ning; Suo, Hong-Bo; Wang, Xi-Chang; Deng, Yun-Hua; Shan, Fei-Hu; Li, Jian-Quan

    2014-02-01

    A Zn modified amorphous-nanocrystalline coating was fabricated on a Ti-6Al-4V alloy by laser cladding of the Co-Ti-B4C-Zn-Y2O3 mixed powders. Such coating was researched by means of a scanning electron microscope (SEM) and a high resolution transmission electron microscope (HRTEM), etc. Experimental results indicated that the Co5Zn21 and TiB2 nanocrystalline phases were produced through in situ metallurgical reactions, which blocked the motion of dislocation, and TiB2 grew along (010), (111) and (024). The Co5Zn21 nanocrystals were produced attached to the ceramics, which mainly consisted of the Co nanoparticles embedded in a heterogeneous zinc, and had varied crystalline orientations.

  19. Effect of annealing on structural and magnetic properties of Al substituted nanocrystalline Fe-Si-Co alloy powders

    NASA Astrophysics Data System (ADS)

    Shyni, P. C.; Alagarsamy, Perumal

    2016-11-01

    We report effects of annealing and substitution of Al on structural and magnetic properties of nanocrystalline Fe80-xAlxCo5Si15 (x=0-10) alloy powders prepared by mechanical alloying process using a planetary ball mill technique. All the as-milled powders exhibit non-equilibrium solid solution of α-Fe (Si,Co,Al). While the average size of crystals decreases, the lattice constant and dislocation density increase with increasing Al content. On the other hand, the annealing at elevated temperatures increases the size of the crystals and decreases the dislocation density. In addition, the substitution of Al in FeAlCoSi alloy powders controls growth of the crystals during annealing. As a result, coercivity (HC) of the annealed powders decreases considerably. However, the variation in HC is dominated by the dislocation density. Fe70Al10Co5Si15 powder annealed at 900 °C exhibits improved magnetic properties (HC~14 Oe and moderate magnetization of 160 emu/g) due to optimum nanocrystalline microstructure with fine nanocrystals (~18 nm) and reduced dislocation density. Systematic correlations observed between structural and magnetic properties for Fe80-xAlxCo5Si15 powders reveal a promising approach to control the growth of the crystals in the annealed nanocrystalline alloys and to improve the magnetic properties of mechanically alloyed Fe-Si based nanocrystalline alloys by adding suitable substituting elements.

  20. Industrialization of nanocrystalline Fe-Si-B-P-Cu alloys for high magnetic flux density cores

    NASA Astrophysics Data System (ADS)

    Takenaka, Kana; Setyawan, Albertus D.; Sharma, Parmanand; Nishiyama, Nobuyuki; Makino, Akihiro

    2016-03-01

    Nanocrystalline Fe-Si-B-P-Cu alloys exhibit high saturation magnetic flux density (Bs) and extremely low magnetic core loss (W), simultaneously. Low amorphous-forming ability of these alloys hinders their application potential in power transformers and motors. Here we report a solution to this problem. Minor addition of C is found to be effective in increasing the amorphous-forming ability of Fe-Si-B-P-Cu alloys. It allows fabrication of 120 mm wide ribbons (which was limited to less than 40 mm) without noticeable degradation in magnetic properties. The nanocrystalline (Fe85.7Si0.5B9.5P3.5Cu0.8)99C1 ribbons exhibit low coercivity (Hc)~4.5 A/m, high Bs~1.83 T and low W~0.27 W/kg (@ 1.5 T and 50 Hz). Success in fabrication of long (60-100 m) and wide (~120 mm) ribbons, which are made up of low cost elements is promising for mass production of energy efficient high power transformers and motors

  1. Magnetocaloric response of amorphous and nanocrystalline Cr-containing Vitroperm-type alloys

    NASA Astrophysics Data System (ADS)

    Moreno-Ramírez, L. M.; Blázquez, J. S.; Franco, V.; Conde, A.; Marsilius, M.; Budinsky, V.; Herzer, G.

    2016-07-01

    The broad compositional range in which transition metal (TM) based amorphous alloys can be obtained, yields an easily tunable magnetocaloric effect (MCE) in a wide temperature range. In some TM-based alloys, anomalous behaviors are reported, as a non-monotonous trend with magnetic moment (e.g. FeZrB alloys). Moreover, in certain Cr-containing Vitroperm alloys anomalously high values of the magnetic entropy change were published. In this work, a systematic study on MCE response of Cr-containing amorphous alloys of composition Fe74-xCrxCu1Nb3Si15.5B6.5 (with x=2, 8, 10, 12, 13, 14 and 20) has been performed in a broad Curie temperature range from 100 K to 550 K. Curie temperature and magnetic entropy change peak of the amorphous alloys decrease with the increase of Cr content at rates of -25.6 K/at% Cr and -54 mJ kg-1 K-1/at% Cr, respectively, following a linear trend with the magnetic moment in both cases. The presence of nanocrystalline phases has been considered as a possible cause in order to explain the anomalies. The samples were nanocrystallized in different stages, however, the magnetocaloric response decreases as crystallization progresses due to the large separation of the Curie temperatures of the two phases.

  2. Nanocrystalline CuNi alloys: improvement of mechanical properties and thermal stability

    NASA Astrophysics Data System (ADS)

    Nogues, Josep; Varea, A.; Pellicer, E.; Sivaraman, K. M.; Pane, S.; Nelson, B. J.; Surinach, S.; Baro, M. D.; Sort, J.

    2014-03-01

    Nanocrystalline metallic films are known to benefit from novel and enhanced physical and chemical properties. In spite of these outstanding properties, nanocrystalline metals typically show relatively poor thermal stability which leads to deterioration of the properties due to grain coarsening. We have studied nanocrystalline Cu1-xNix (0.56 < x < 1) thin films (3 μm-thick) electrodeposited galvanostatically onto Cu/Ti/Si (100) substrates. CuNi thin films exhibit large values of hardness (6.15 < H < 7.21 GPa), which can be tailored by varying the composition. However, pure Ni films (x = 1) suffer deterioration of their mechanical and magnetic properties after annealing during 3 h at relatively low temperatures (TANN > 475 K) due to significant grain growth. Interestingly, alloying Ni with Cu clearly improves the thermal stability of the material because grain coarsening is delayed due to segregation of a Cu-rich phase at grain boundaries, thus preserving both the mechanical and magnetic properties up to higher TANN.

  3. Nanocrystalline Hydroxyapatite/Si Coating by Mechanical Alloying Technique

    PubMed Central

    Hannora, Ahmed E.; Mukasyan, Alexander S.; Mansurov, Zulkhair A.

    2012-01-01

    A novel approach for depositing hydroxyapatite (HA) films on titanium substrates by using mechanical alloying (MA) technique has been developed. However, it was shown that one-hour heat treatment at 800°C of such mechanically coated HA layer leads to partial transformation of desired HA phase to beta-tri-calcium phosphate (β-TCP) phase. It appears that the grain boundary and interface defects formed during MA promote this transformation. It was discovered that doping HA by silicon results in hindering this phase transformation process. The Si-doped HA does not show phase transition to β-TCP or decomposition after heat treatment even at 900°C. PMID:22312324

  4. Comparison of high frequency, high temperature core loss and B-H loop characteristics of an 80 Ni-Fe crystalline alloy and two iron-based amorphous alloys

    NASA Technical Reports Server (NTRS)

    Wieserman, William R.; Schwarze, Gene E.; Niedra, Janis M.

    1991-01-01

    Limited experimental data exists for the specific core loss and dynamic B-H loops for soft magnetic materials for the combined conditions of high frequency and high temperature. This experimental study investigates the specific core loss and dynamic B-H characteristics of a nickel-iron crystalline magnetic alloy (Supermalloy) and two iron-based amorphous magnetic materials (Metglas 2605S-3A and Metglas 2605SC) over the frequency range of 1-50 kHz and temperature range of 23-300 C under sinusoidal voltage excitation. The effects of maximum magnetic flux density, frequency, and temperature on the specific core loss and on the size and shape of the B-H loops are examined. The Supermalloy and Metglass 2605S-3A and 2605SC data are used to compare the core loss of transformers with identical kVA and voltage ratings.

  5. Anisotropic nanolaminated CoNiFe cores integrated into microinductors for high-frequency dc-dc power conversion

    NASA Astrophysics Data System (ADS)

    Kim, Jooncheol; Kim, Minsoo; Kim, Jung-Kwun; Herrault, Florian; Allen, Mark G.

    2015-11-01

    This paper presents a rectangular, anisotropic nanolaminated CoNiFe core that possesses a magnetically hard axis in the long geometric axis direction. Previously, we have developed nanolaminated cores comprising tens to hundreds of layers of 300-1000 nm thick metallic alloys (i.e. Ni80Fe20 or Co44Ni37Fe19) based on sequential electrodeposition, demonstrating suppressed eddy-current losses at MHz frequencies. In this work, magnetic anisotropy was induced to the nanolaminated CoNiFe cores by applying an external magnetic field (50-100 mT) during CoNiFe film electrodeposition. The fabricated cores comprised tens to hundreds of layers of 500-1000 nm thick CoNiFe laminations that have the hard-axis magnetic property. Packaged in a 22-turn solenoid test inductor, the anisotropic core showed 10% increased effective permeability and 25% reduced core power losses at MHz operation frequency, compared to an isotropic core of the identical geometry. Operating the anisotropic nanolaminated CoNiFe core in a step-down dc-dc converter (15 V input to 5 V output) demonstrated 81% converter efficiency at a switching frequency of 1.1 MHz and output power of 6.5 W. A solenoid microinductor with microfabricated windings integrated with the anisotropic nanolaminated CoNiFe core was fabricated, demonstrating a constant inductance of 600 nH up to 10 MHz and peak quality factor exceeding 20 at 4 MHz. The performance of the microinductor with the anisotropic nanolaminated CoNiFe core is compared with other previously reported microinductors.

  6. Magnetoelectric coupling characteristics in multiferroic heterostructures with different thickness of nanocrystalline soft magnetic alloy

    NASA Astrophysics Data System (ADS)

    Chen, Lei; Wang, Yao

    2016-05-01

    Magnetoelectric(ME) coupling characteristics in multiferroic heterostructures with different thickness of nanocrystalline soft magnetic alloy has been investigated at low frequency. The ME response with obvious hysteresis, self-biased and dual-peak phenomenon is observed for multiferroic heterostructures, which results from strong magnetic interactions between two ferromagnetic materials with different magnetic properties, magnetostrictions and optimum bias magnetic fields Hdc,opti. The proposed multiferroic heterostructures not only enhance ME coupling significantly, but also broaden dc magnetic bias operating range and overcomes the limitations of narrow bias range. By optimizing the thickness of nanocrystalline soft magnetic alloy Tf, a significantly zero-biased ME voltage coefficient(MEVC) of 14.8mV/Oe (185 mV/cmṡ Oe) at Tf = 0.09 mm can be obtained, which is about 10.8 times as large as that of traditional PZT/Terfenol-D composite with a weak ME coupling at zero bias Hdc,zero. Furthermore, when Tf increases from 0.03 mm to 0.18 mm, the maximum MEVC increases nearly linearly with the increased Tf at Hdc,opti. Additionally, the experimental results demonstrate the ME response for multiferroic heterostructures spreads over a wide magnetic dc bias operating range. The excellent ME performance provides a promising and practicable application for both highly sensitive magnetic field sensors without bias and ME energy harvesters.

  7. Phase transformation during mechano-synthesis of nanocrystalline/amorphous Fe–32Mn–6Si alloys

    SciTech Connect

    Amini, Rasool; Shamsipoor, Ali; Ghaffari, Mohammad; Alizadeh, Morteza; Okyay, Ali Kemal

    2013-10-15

    Mechano-synthesis of Fe–32Mn–6Si alloy by mechanical alloying of the elemental powder mixtures was evaluated by running the ball milling process under an inert argon gas atmosphere. In order to characterize the as-milled powders, powder sampling was performed at predetermined intervals from 0.5 to 192 h. X-ray florescence analyzer, X-ray diffraction, scanning electron microscope, and high resolution transmission electron microscope were utilized to investigate the chemical composition, structural evolution, morphological changes, and microstructure of the as-milled powders, respectively. According to the results, the nanocrystalline Fe–Mn–Si alloys were completely synthesized after 48 h of milling. Moreover, the formation of a considerable amount of amorphous phase during the milling process was indicated by quantitative X-ray diffraction analysis as well as high resolution transmission electron microscopy image and its selected area diffraction pattern. It was found that the α-to-γ and subsequently the amorphous-to-crystalline (especially martensite) phase transformation occurred by milling development. - Graphical abstract: Mechano-synthesis of nanocrystalline/amorphous Fe–32Mn–6Si shape memory alloys in the powder form: amorphous phase formation, α-to-γ phase transformation, mechano-crystallization of the amorphous, and martensite phase formation during the process. Highlights: • During MA, the α-to-γ phase transformation and amorphization occurred. • Mechano-crystallization of the amorphous phase occurred at sufficient milling time. • The formation of high amount of ε-martensite was evidenced at high milling times. • The platelet, spherical, and then irregular particle shapes was extended by MA. • By MA, the particles size was increased, then reduced, and afterward re-increased.

  8. Development of FeSiBNbCu Nanocrystalline Soft Magnetic Alloys with High B s and Good Manufacturability

    NASA Astrophysics Data System (ADS)

    Wan, Fangpei; He, Aina; Zhang, Jianhua; Song, Jiancheng; Wang, Anding; Chang, Chuntao; Wang, Xinmin

    2016-10-01

    In order to develop Fe-based nanocrystalline soft magnetic alloys with high saturation magnetic flux density ( B s) and good manufacturability, the effect of the Nb content on the thermal stability, microstructural evolution and soft magnetic properties of Fe78- x Si13B8Nb x Cu1 ( x = 0, 1, 2 and 3) alloys were investigated. It is found that proper Nb addition is effective in widening the optimum annealing temperature range and refining the α-Fe grain in addition to enhancing the soft magnetic properties. For the representative Fe76 Si13B8Nb2Cu1 alloy, the effective annealing time can be over 60 min in the optimal temperature range of 500-600°C. FeSiBNbCu nanocrystalline soft magnetic alloys with desirable soft magnetic properties including high B s of 1.39 T, low coercivity ( H c) of 1.5 A/m and high effective permeability ( μ e) of 21,500 at 1 kHz have been developed. The enhanced soft magnetic performance and manufacturability of the FeSiBNbCu nanocrystalline alloys are attributed to the high activated energy for the precipitation of α-Fe(Si) and the second phase. These alloys with excellent performance have promising applications in electromagnetic fields like inductors.

  9. Development of FeSiBNbCu Nanocrystalline Soft Magnetic Alloys with High B s and Good Manufacturability

    NASA Astrophysics Data System (ADS)

    Wan, Fangpei; He, Aina; Zhang, Jianhua; Song, Jiancheng; Wang, Anding; Chang, Chuntao; Wang, Xinmin

    2016-06-01

    In order to develop Fe-based nanocrystalline soft magnetic alloys with high saturation magnetic flux density (B s) and good manufacturability, the effect of the Nb content on the thermal stability, microstructural evolution and soft magnetic properties of Fe78-x Si13B8Nb x Cu1 (x = 0, 1, 2 and 3) alloys were investigated. It is found that proper Nb addition is effective in widening the optimum annealing temperature range and refining the α-Fe grain in addition to enhancing the soft magnetic properties. For the representative Fe76 Si13B8Nb2Cu1 alloy, the effective annealing time can be over 60 min in the optimal temperature range of 500-600°C. FeSiBNbCu nanocrystalline soft magnetic alloys with desirable soft magnetic properties including high B s of 1.39 T, low coercivity (H c) of 1.5 A/m and high effective permeability (μ e) of 21,500 at 1 kHz have been developed. The enhanced soft magnetic performance and manufacturability of the FeSiBNbCu nanocrystalline alloys are attributed to the high activated energy for the precipitation of α-Fe(Si) and the second phase. These alloys with excellent performance have promising applications in electromagnetic fields like inductors.

  10. Investigating the Thermal and Phase Stability of Nanocrystalline Ni-W Produced by Electrodeposition, Sputtering, and Mechanical Alloying

    NASA Astrophysics Data System (ADS)

    Marvel, Christopher Jonathan

    The development of nanocrystalline materials has been increasingly pursued over the last few decades. They have been shown to exhibit superior properties compared to their coarse-grain counterparts, and thus present a tremendous opportunity to revolutionize the performance of nanoscale devices or bulk structural materials. However, nanocrystalline materials are highly prone to grain growth, and if the nanocrystalline grains coarsen, the beneficial properties are lost. There is a strong effort to determine the most effective thermal stability mechanisms to avoid grain growth, but the physical nature of nanocrystalline grain growth is still unclear due to a lack of detailed understanding of nanocrystalline microstructures. Furthermore, the influence of contamination has scarcely been explored with advanced transmission electron microscopy techniques, nor has there been a direct comparison of alloys fabricated with different bulk processes. Therefore, this research has applied aberration-corrected scanning transmission electron microscopy to characterize nanocrystalline Ni-W on the atomic scale and elucidate the physical grain growth behavior. Three primary objectives were pursued: (1) explore the thermal stability mechanisms of nanocrystalline Ni-W, (2) evaluate the phase stability of Ni-W and link any findings to grain growth behavior, and (3) compare the influences of bulk fabrication processing, including electrodeposition, DC magnetron sputtering, and mechanical alloying, on the thermal stability and phase stability of Ni-W. Several thermal stability mechanisms were identified throughout the course of this research. First and foremost, W-segregation was scarcely observed to grain boundaries, and it is unclear if W-segregation improves thermal stability contrary to most reports in the 2 literature. Long-range Ni4W chemical ordering was observed in alloys with more than 20 at.% W, and it is likely Ni4W domains reduce grain boundary mobility. In addition, lattice

  11. Electrodeposited Nanolaminated CoNiFe Cores for Ultracompact DC-DC Power Conversion

    SciTech Connect

    Kim, J; Kim, M; Herrault, F; Park, JY; Allen, MG

    2015-09-01

    Laminated metallic alloy cores (i.e., alternating layers of thin film metallic alloy and insulating material) of appropriate lamination thickness enable suppression of eddy current losses at high frequencies. Magnetic cores comprised of many such laminations yield substantial overall magnetic volume, thereby enabling high-power operation. Previously, we reported nanolaminated permalloy (Ni-80 Fe-20) cores based on a sequential electrodeposition technique, demonstrating negligible eddy current losses at peak flux densities up to 0.5 T and operating at megahertz frequencies. This paper demonstrates improved performance of nanolaminated cores comprising tens to hundreds of layers of 300-500-nm-thick CoNiFe films that exhibit superior magnetic properties (e.g., higher saturation flux density and lower coercivity) than permalloy. Nanolaminated CoNiFe cores can be operated up to a peak flux density of 0.9 T, demonstrating improved power handling capacity and exhibiting 30% reduced volumetric core loss, attributed to lowered hysteresis losses compared to the nanolaminated permalloy core of the same geometry. Operating these cores in a buck dc-dc power converter at a switching frequency of 1 MHz, the nanolaminated CoNiFe cores achieved a conversion efficiency exceeding 90% at output power levels up to 7 W, compared to an achieved permalloy core conversion efficiency below 86% at 6 W.

  12. Magnetic properties and structure of nanocrystalline FINEMET alloys with various iron contents

    NASA Astrophysics Data System (ADS)

    Mushnikov, N. V.; Potapov, A. P.; Shishkin, D. A.; Protasov, A. V.; Golovnya, O. A.; Shchegoleva, N. N.; Gaviko, V. S.; Shunyaev, K. Yu.; Bykov, V. A.; Starodubtsev, Yu. N.; Belozerov, V. Ya.

    2015-07-01

    The effect of the composition and annealing temperature on the structure and magnetic properties of soft magnetic nanocrystalline Fe-Cu-Nb-Mo-Si-B alloys has been studied. An increase in the iron content compared to that in the traditional FINEMET alloy is shown to allow one to increase the magnetic induction by 18% at a coercive force of no less than 6 A/m. It has been found that, along with the amorphous phase, rapidly quenched ribbons of alloys enriched in Fe contain crystalline α-Fe-based phase precipitates, the (100) crystallographic directions of which are perpendicular to the ribbon plane. Thermomagnetic analysis and differential scanning calorimetry were used to determine the temperatures of structural and magnetic phase transformations of the alloys with different iron contents. It was found that the separation of amorphous phase into areas of different compositions precedes the precipitation of nano-sized soft magnetic Fe-Si phase grains in the rapidly quenched iron-enriched ribbons.

  13. Characterization of Nanocrystalline Nickel-Cobalt Alloys Synthesized by Direct and Pulse Electrodeposition

    NASA Astrophysics Data System (ADS)

    Salehi, M.; Saidi, A.; Ahmadian, M.; Raeissi, K.

    2014-01-01

    Nanocrystalline Ni-Co alloys are electrodeposited by direct (DC) and pulse current (PC) in an electrolyte solution which consisted of nickel sulfate, cobalt sulfate and boric acid. Electrodeposition parameters including current density, electrolyte pH and pulse times in a single electrolyte bath were changed. XRD pattern showed that the structure of the alloys depends on Co content and the synthesis parameter and changed from single phase structure (fcc) to dual phase structure (fcc + hcp). The Co content in the deposited alloys declined from 70 at.% to 50 at.% by increasing in direct current from 70 mA/cm2 to 115 mA/cm2 and also decreased from 75 at.% to 33 at.% with decrease in pH values from 4 to 2. By applying PC the Co content changed from 76 at.% to 41 at.%. Magnetic properties measurements showed the saturation magnetization (Ms) increased with increasing the Co content. There was no significant effect on coercivity values (Hc) with change in Co content and about 40 Oe was obtained for all samples. The grain size of deposited alloys obtained between 24-58 nm and 15-21 nm by applying DC and PC, respectively.

  14. 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. PMID:17715984

  15. Thermal Stabilization and Mechanical Properties of Nanocrystalline Iron-Nickel-Zirconium Alloys

    NASA Astrophysics Data System (ADS)

    Kotan, Hasan

    Ultrafine grained and nanostructured materials are promising for structural applications because of the high strength compared to coarse grained counterparts. However, their widespread application is limited by an inherently high driving force for thermally induced grain growth, even at low temperatures. Accordingly, the understanding of and control over grain growth in nanoscale materials is of great technological and scientific importance as many physical properties (i.e. mechanical properties) are functions of the average grain size and the grain size distribution within the microstructure. Here, we investigate the microstructural evolution and grain growth in Fe-Ni alloys with Zr addition and differentiate the stabilization mechanisms acting on grain boundaries. Fe-Ni alloys are chosen for stability investigations since they are important for understanding the behavior of many steels and other ferrous alloys. Zirconium is proven to be an effective grain size stabilizer in pure Fe and Fe-base systems. In this study, nanocrystalline alloys were prepared by high energy ball milling. In situ and ex situ experiments were utilized to directly follow grain growth and microstructural evolution as a function of temperature and composition. The information obtained from these experiments enables the real time observation of microstructural evolution and phase transformation and provides a unique view of dynamic reactions as they occur. The knowledge of the thermal stability will exploit the potential high temperature applications and the consolidation conditions (i.e. temperature and pressure) to obtain high dense materials for advanced mechanical tests. Our investigations reveal that the grain growth of Fe-Ni alloys is not affected by Ni content but strongly inhibited by the addition of 1 at% Zr up to about 700 °C. The microstructural stability is lost due to the bcc-to-fcc transformation (occurring at 700°C) by the sudden appearance of abnormally grown fcc grains

  16. Characterization of Magnetic NiFe Nanoparticles with Controlled Bimetallic Composition

    SciTech Connect

    Liu, Yan; Chi, Yanxiu; Shan, Shiyao; Yin, Jun; Luo, Jin; Zhong, Chuan-Jian

    2014-02-25

    The exploration of the magnetic properties of bimetallic alloy nanoparticles for various technological applications requires the ability to control the morphology, composition, and surface properties. In this report, we describe new findings of an investigation of the morphology and composition of NiFe alloy nanoparticles synthesized under controlled conditions. The controllability over the bimetallic composition has been demonstrated by the observation of an approximate linear relationship between the composition in the nanoparticles and in the synthetic feeding. The morphology of the NiFe nanoparticles is consistent with an fcc-type alloy, with the lattice strain increasing linearly with the iron content in the nanoparticles. The alloy nanoparticles exhibit remarkable resistance to air oxidation in comparison with Ni or Fe particles. The thermal stability and the magnetic properties of the as-synthesized alloy nanoparticles are shown to depend on the composition. The alloy nanoparticles have also be sown to display low saturation magnetization and coercivity values in comparison with the Ni nanoparticles, in line with the superparamagnetic characteristic. These findings have important implications for the design of stable and controllable magnetic nanoparticles for various technological applications.

  17. Effect of Nano-crystalline Ceramic Coats Produced by Plasma Electrolytic Oxidation on Corrosion Behavior of AA5083 Aluminum Alloy

    NASA Astrophysics Data System (ADS)

    Thayananth, T.; Muthupandi, V.; Rao, S. R. Koteswara

    2010-10-01

    High specific strength offered by aluminum and magnesium alloys makes them desirable in modern transportation industries. Often the restrictions imposed on the usage of these alloys are due to their poor tribological and corrosion properties. However, their corrosion properties can be further enhanced by synthesizing ceramic coating on the substrate through Plasma Electrolytic Oxidation (PEO) process. In this study, nano-crystalline alumina coatings were formed on the surface of AA5083 aluminum alloy test coupons using PEO process in aqueous alkali-silicate electrolyte with and without addition of sodium aluminate. X-ray diffraction (XRD) studies showed that the crystallite size varied between 38 and 46 nm and α- and γ- alumina were the dominant phases present in the coatings. Corrosion studies by potentiodynamic polarization tests in 3.5% NaCl revealed that the electrolyte composition has an influence on the corrosion resistance of nano-crystalline oxide layer formed.

  18. Formation of Nanocrystalline Surface of Cu-Sn Alloy Foam Electrochemically Produced for Li-Ion Battery Electrode.

    PubMed

    Ye, Bora; Kim, Sunjung

    2015-10-01

    Cu-Sn alloy foam is a promising electrode material for Li-ion batteries. In this study, Cu-Sn alloy foam was produced by diffusion-limited electrodeposition in alkaline electrolyte using polyurethane (PU) foam template. Our major concern is to form Cu-Sn alloy foam with nanocrystalline surface morphology by adjusting electrodeposition conditions such as deposition potential and metal ion concentration. Cu-Sn alloy layers comprising of nanoclusters such as nanospheres, nanoellipsoids, and nanoflakes were created depending on electrodeposition conditions. Larger surface area of nanocluster-interconnected Cu-Sn alloy layer was created when both Sn concentration and negative deposition potential were higher. After decomposing PU template thermally, Cu-Sn alloy foam of Cu, Cu6Sn5, and Cu3Sn phases was finally produced. PMID:26726491

  19. Anti-wear properties of Cr C and Ni Co alloy coatings as substitutes for conventional nanocrystalline Cr coatings

    NASA Astrophysics Data System (ADS)

    Zeng, Zhixiang; Zhang, Junyan

    2008-09-01

    Nanocrystalline Ni-Co, amorphous Cr-C alloy and nanocrystalline Cr-C coatings were electrodeposited from 'environmentally acceptable' electrolytes as potential substitutes for conventional nanocrystalline Cr coatings electrodeposited from noxious hexavalent chromium. The structure, morphology and hardness of coatings are investigated using a transmission electron microscope, a scanning electronic microscope and a Vickers hardness tester, respectively. Anti-wear properties are tested on a pin-on-plate vibrant wear tester. The correlation between the wear resistance, hardness, brittleness and the lubricated state is investigated. The results show that the wear behaviour of specimens significantly depends on their lubricated state, hardness and brittleness. Under the lubricated sliding condition, abrasive wear is the primary wear mechanism for all specimens. With respect to the abrasive wear mechanism, both the elastic and plastic deformations play important roles during the lubricated sliding process. Thus, the amorphous and nanocrystalline Cr-C alloy coatings, with both high brittleness and high hardness, exhibit a lower wear rate than the conventional Cr and Ni-Co coatings. On the other hand, under the dry sliding condition, the annealed Ni-Co coating, with an excellent compromise between high hardness and toughness, exhibits an abrasive wear mechanism and a relatively low wear rate; in contrast, the brittle Cr-matrix coatings exhibit a severe fatigue/delamination wear mechanism and high wear rate.

  20. The generation of wear-resistant antimicrobial stainless steel surfaces by active screen plasma alloying with N and nanocrystalline Ag.

    PubMed

    Dong, Yangchun; Li, Xiaoying; Sammons, Rachel; Dong, Hanshan

    2010-04-01

    Hospital-acquired infections (HAIs), a large proportion of which are derived from contact transmission, represent a massive global challenge. In this study a novel active screen plasma (ASP) alloying technology has been developed to generate highly durable antimicrobial surfaces by combining a wear-resistant S-phase with nanocrystalline silver for medical grade stainless steel. The phase constituent, microstructure, composition and surface roughness of the alloyed surfaces were fully characterized, and the surface hardness, wear resistance and antimicrobial efficiency of the treated surfaces were evaluated. Experimental results showed that the surface hardness and sliding wear resistance of medical grade 316LVM stainless steel can be effectively improved by the ASP alloying treatment; furthermore, the Ag alloyed S-phase can achieve 93% reduction in Escherichia coli (E. coli) after 6 h contact time. Therefore, the novel ASP alloying treatment can not only improve wear resistance but also confer antibacterial activity to stainless steel surfaces.

  1. Low-frequency creep in CoNiFe films.

    NASA Technical Reports Server (NTRS)

    Bartran, D. S.; Bourne, H. C., Jr.; Chow, L. G.

    1972-01-01

    Domain wall motion excited by slow rise-time, bipolar, hard-axis pulses in vacuum deposited CoNiFe films from 1500 to 2000 A thick is studied. The results are consistent with those of comparable NiFe films. Furthermore, the wall coercivity is found to be the most significant sample property correlated to the low-frequency creep properties of all the samples.

  2. Comparative Study of Thermal Stability of NiFe and NiFeTa Thin Films Grown by Cosputtering Technique

    NASA Astrophysics Data System (ADS)

    Phuoc, Nguyen N.; Ong, C. K.

    2016-08-01

    A comparative study of the thermal behavior of dynamic permeability spectra for compositionally graded NiFeTa and uniform-composition NiFe thin films has been carried out. We found that the resonance frequency of the compositionally graded NiFeTa film increased with increasing temperature, while it decreased for the case of the uniform-composition NiFe thin film. This finding unambiguously suggests that the compositional gradient of the film is the only reason for the increase of the magnetic anisotropy with temperature due to its stress-induced origin, while the cosputtering technique does not play any role in this peculiar behavior. The temperature dependence of the frequency linewidth is also presented and discussed.

  3. Formation and analysis of amorphous and nanocrystalline phases in Al-Cu-Mg alloy under friction stir processing

    NASA Astrophysics Data System (ADS)

    Liu, Peng; Shi, Qing-yu

    2015-06-01

    Homogeneous amorphous and nanocrystalline phases formed in the nugget zone of a friction stir-processed Al-Cu-Mg alloy have been studied. X-ray diffraction analysis indicated a diffuse scattering peak with characteristics of an amorphous phase existed in the range 15°-29°. Further, TEM analysis proved the existence of an amorphous structure. Friction stir processing provides special physical conditions, such as high temperature, high hydrostatic pressure and large shear stress, which could induce the amorphization of the alloy.

  4. Investigation of (Fe,Co)NbB-Based Nanocrystalline Soft Magnetic Alloys by Lorentz Microscopy and Off-Axis Electron Holography.

    PubMed

    Zheng, Changlin; Kirmse, Holm; Long, Jianguo; Laughlin, David E; McHenry, Michael E; Neumann, Wolfgang

    2015-04-01

    The relationship between microstructure and magnetic properties of a (Fe,Co)NbB-based nanocrystalline soft magnetic alloy was investigated by analytical transmission electron microscopy (TEM). The microstructures of (Fe0.5Co0.5)80Nb4B13Ge2Cu1 nanocrystalline alloys annealed at different temperatures were characterized by TEM and electron diffraction. The magnetic structures were analyzed by Lorentz microscopy and off-axis electron holography, including quantitative measurement of domain wall width, induction, and in situ magnetic domain imaging. The results indicate that the magnetic domain structure and particularly the dynamical magnetization behavior of the alloys strongly depend on the microstructure of the nanocrystalline alloys. Smaller grain size and random orientation of the fine particles decrease the magneto-crystalline anisotropy and suggests better soft magnetic properties which may be explained by the anisotropy model of Herzer.

  5. Amperometric hydrogen peroxide and glucose biosensor based on NiFe2/ordered mesoporous carbon nanocomposites.

    PubMed

    Xiang, Dong; Yin, Longwei; Ma, Jingyun; Guo, Enyan; Li, Qun; Li, Zhaoqiang; Liu, Kegao

    2015-01-21

    Nanocomposites of NiFex embedded in ordered mesoporous carbon (OMC) (x = 0, 1, 2) were prepared by a wet impregnation and hydrogen reduction process and were used to construct electrochemical biosensors for the amperometric detection of hydrogen peroxide (H2O2) or glucose. The NiFe2/OMC nanocomposites were demonstrated to have a large surface area, suitable mesoporous channels, many edge-plane-like defective sites, and a good distribution of alloyed nanoparticles. The NiFe2/OMC and Nafion modified glass carbon electrode (GCE) exhibited excellent electrocatalytic activities toward the reduction of H2O2 as well. By utilizing it as a bioplatform, GOx (glucose oxidase) cross-linked with Nafion was immobilized on the surface of the electrode for the construction of an amperometric glucose biosensor. Our results indicated that the amperometric hydrogen peroxide biosensor (NiFe2/OMC + Nafion + GCE) showed good analytical performances in term of a high sensitivity of 4.29 μA mM(-1) cm(-2), wide linearity from 6.2 to 42,710 μM and a low detection limit of 0.24 μM at a signal-to-noise ratio of 3 (S/N = 3). This biosensor exhibited excellent selectivity, high stability and negligible interference for the detection of H2O2. In addition, the immobilized enzyme on NiFe2/OMC + Nafion + GCE, retaining its bioactivity, exhibited a reversible two-proton and two-electron transfer reaction, a fast heterogeneous electron transfer rate and an effective Michaelis-Menten constant (K) (3.18 mM). The GOx + NiFe2/OMC + Nafion + GCE could be used to detect glucose based on the oxidation of glucose catalyzed by GOx and exhibited a wide detection range of 48.6-12,500 μM with a high sensitivity of 6.9 μA mM(-1) cm(-2) and a low detection limit of 2.7 μM (S/N = 3). The enzymic biosensor maintained a high selectivity and stability features, and shows great promise for application in the detection of glucose.

  6. Amperometric hydrogen peroxide and glucose biosensor based on NiFe2/ordered mesoporous carbon nanocomposites.

    PubMed

    Xiang, Dong; Yin, Longwei; Ma, Jingyun; Guo, Enyan; Li, Qun; Li, Zhaoqiang; Liu, Kegao

    2015-01-21

    Nanocomposites of NiFex embedded in ordered mesoporous carbon (OMC) (x = 0, 1, 2) were prepared by a wet impregnation and hydrogen reduction process and were used to construct electrochemical biosensors for the amperometric detection of hydrogen peroxide (H2O2) or glucose. The NiFe2/OMC nanocomposites were demonstrated to have a large surface area, suitable mesoporous channels, many edge-plane-like defective sites, and a good distribution of alloyed nanoparticles. The NiFe2/OMC and Nafion modified glass carbon electrode (GCE) exhibited excellent electrocatalytic activities toward the reduction of H2O2 as well. By utilizing it as a bioplatform, GOx (glucose oxidase) cross-linked with Nafion was immobilized on the surface of the electrode for the construction of an amperometric glucose biosensor. Our results indicated that the amperometric hydrogen peroxide biosensor (NiFe2/OMC + Nafion + GCE) showed good analytical performances in term of a high sensitivity of 4.29 μA mM(-1) cm(-2), wide linearity from 6.2 to 42,710 μM and a low detection limit of 0.24 μM at a signal-to-noise ratio of 3 (S/N = 3). This biosensor exhibited excellent selectivity, high stability and negligible interference for the detection of H2O2. In addition, the immobilized enzyme on NiFe2/OMC + Nafion + GCE, retaining its bioactivity, exhibited a reversible two-proton and two-electron transfer reaction, a fast heterogeneous electron transfer rate and an effective Michaelis-Menten constant (K) (3.18 mM). The GOx + NiFe2/OMC + Nafion + GCE could be used to detect glucose based on the oxidation of glucose catalyzed by GOx and exhibited a wide detection range of 48.6-12,500 μM with a high sensitivity of 6.9 μA mM(-1) cm(-2) and a low detection limit of 2.7 μM (S/N = 3). The enzymic biosensor maintained a high selectivity and stability features, and shows great promise for application in the detection of glucose. PMID:25429370

  7. Microstructure of the Al-La-Ni-Fe system

    SciTech Connect

    Vasil’ev, A. L.; Ivanova, A. G.; Bakhteeva, N. D.; Kolobylina, N. N.; Orekhov, A. S.; Presnyakov, M. Yu.; Todorova, E. V.

    2015-01-15

    The microstructure of alloys based on the Al-La-Ni-Fe system, which are characterized by a unique ability to form metal glasses and nanoscale composites in a wide range of compositions, has been investigated. Al{sub 85}Ni{sub 7}Fe{sub 4}La{sub 4} and Al{sub 85}Ni{sub 9}Fe{sub 2}La{sub 4} alloys have been analyzed by electron microscopy (including high-resolution scanning transmission electron microscopy), energy-dispersive X-ray microanalysis, electron diffraction (ED), and X-ray diffraction (XRD). It is found that, along with fcc Al and Al{sub 4}La (Al{sub 11}La{sub 3}) particles, these alloys contain a ternary phase Al{sub 3}Ni{sub 1−x}Fe{sub x} (sp. gr. Pnma) isostructural to the Al{sub 3}Ni phase and a quaternary phase Al{sub 8}Fe{sub 2−x}Ni{sub x}La isostructural to the Al{sub 8}Fe{sub 2}Eu phase (sp. gr. Pbam). The unit-cell parameters of the Al{sub 3}Ni{sub 1−x}Fe{sub x} and Al{sub 8}Fe{sub 2−x}Ni{sub x}La compounds, determined by ED and refined by XRD, are a = 0.664(1) nm, b = 0.734(1) nm, and c = 0.490(1) nm for Al{sub 3}Ni{sub 1−x}Fe{sub x} and a = 1.258(3) nm, b = 1.448(3) nm, and c = 0.405(8) nm for Al{sub 8}Fe{sub 2−x}Ni{sub x}La. In both cases Ni and Fe atoms are statistically arranged, and no ordering is found. Al{sub 8}Fe{sub 2−x}Ni{sub x}La particles contain inclusions in the form of Al{sub 3}Fe δ layers.

  8. Amorphous and nanocrystalline phase formation in highly-driven Al-based binary alloys

    SciTech Connect

    Kalay, Yunus Eren

    2009-01-01

    each other. This deviation indicates an adiabatic type solidification path where heat of fusion is reabsorbed. It is interesting that this particle size range is also consistent with the appearance of a microcellular growth. While no glass formation is observed within this system, the smallest size powders appear to consist of a mixture of nanocrystalline Si and Al. Al-Sm alloys have been investigated within a composition range of 34 to 42 wt% Sm. Gas atomized powders of Al-Sm are investigated to explore the morphological and structural hierarchy that correlates with different degrees of departure from full equilibrium conditions. The resultant powders show a variety of structural selection with respect to amount of undercooling, with an amorphous structure appearing at the highest cooling rates. Because of the chaotic nature of gas atomization, Cu-block melt-spinning is used to produce a homogeneous amorphous structure. The as-quenched structure within Al-34 to 42 wt% Sm consists of nanocrystalline fcc-Al (on the order of 5 nm) embedded in an amorphous matrix. The nucleation density of fcc-Al after initial crystallization is on the order of 1022-1023m-3, which is 105-106 orders of magnitude higher than what classical nucleation theory predicts. Detailed analysis of liquid and as-quenched structures using high energy synchrotron X-ray diffraction, high energy transmission electron microscopy, and atom probe tomography techniques revealed an Al-Sm network similar in appearance to a medium range order (MRO) structure. A model whereby these MRO clusters promote the observed high nucleation density of fcc-Al nanocrystals is proposed. The devitrification path was identified using high temperature, in-situ, high energy synchrotron X-ray diffraction techniques and the crystallization kinetics were described using an analytical Johnson-Mehl-Avrami (JMA) approach.

  9. Properties Evaluation and Studying Production Mechanism of Nanocrystalline NiAl Intermetallic Compound by Mechanical Alloying

    NASA Astrophysics Data System (ADS)

    Khajesarvi, Ali; Akbari, Golamhossein

    2016-04-01

    Ni50Al50 intermetallic compound was synthesized by mechanical alloying (MA) of elemental mixtures of Ni and Al powders in a planetary ball mill. After 16 hours of milling and obtaining crystallites with a critical size, the initial NiAl compound was formed along with the combustive reaction after opening the vial lid. In the time interval of 16 to 128 hours, the reaction from combustive state reached the explosive state. Finally, after 128 hours of milling, the initial powders were wholly transformed into NiAl before completion of the milling time. Structural changes of powder particles during MA were studied by X-ray diffractometry and scanning electron microscopy. The crystallite size measurements revealed that the grain size of the NiAl phase decreased from 155 to 26 nm with increasing MA time from 8 to 128 hours. Microhardness for nanocrystalline Ni50Al50 intermetallic compound produced after 128 hours of milling was measured as about 350 Hv.

  10. Outstanding efficiency in energy conversion for electric motors constructed by nanocrystalline soft magnetic alloy "NANOMET®" cores

    NASA Astrophysics Data System (ADS)

    Nishiyama, N.; Tanimoto, K.; Makino, A.

    2016-05-01

    Recently updated nanocrystalline soft magnetic Fe-Co-Si-B-P-Cu alloys "NANOMET®" exhibit high saturation magnetic flux density (Bs > 1.8 T), low coercivity (Hc < 10 A/m) and low core loss (W1.7/50 ˜ 0.4 W/kg) even in a ribbon form with a thickness of up to 40 μm. By utilize excellent magnetic softness, several products such as motors or transformers for electrical appliances are now under developing by industry-academia collaboration. In particular, it is found that a brushless DC motor using NANOMET® core exhibited remarkable improvement in energy consumption. The prototype motor with an outer core diameter of 70 mm and a core thickness of 50 mm was constructed using laminated nano-crystallized NANOMET® ribbons. Core-loss for the constructed motor was improved from 1.4 W to 0.4 W only by replacing the non-oriented Si-steel core with NANOMET® one. The overall motor efficiency is evaluated to be 3% improvement. In this work, the relation between processing and resulting magnetic properties will be presented. In addition, feasibility for commercialization will also be discussed.

  11. Microstructural refinement of Al-Si alloy upon ultrasonic nanocrystalline surface modification treatment.

    PubMed

    He, Yinsheng; Li, Kejian; Cho, In Shik; Park, In Gyu; Shin, Keesam

    2014-11-01

    In this work, an Al-7 wt.% Si alloy, which is widely used as the structural materials in the automotive and aerospace industries for their high specific strength, was subjected to ultrasonic nanocrystalline surface modification (UNSM) treatment. After UNSM treatment, the effect of UNSM on the microstructural evolution of both Al grain and the dispersed Si particles was studied by using scanning electron microscope (SEM) and transmission electron microscope (TEM). Experimental results show that the ultra-fine grain (UFG, - 400 nm in size) structure is developed in the top surface layer (up to - 15 μm in depth). The coarse Si particles were refined and well dispersed in the UFG Al matrix. Cross-sectional TEM observation revealed that the grain refinement mechanism involved the formation of new grain boundaries dividing the coarse grain into UFG structure. Nanotwin and nanosize Si were formed within the original coarse Si particles. The presence of dispersed Si particles in the Al matrix accelerated the Al grain refinement process. PMID:25958593

  12. Surface nanocrystalline and hardening effects of Ti-Al-V alloy by electropulsing ultrasonic shock

    NASA Astrophysics Data System (ADS)

    Ye, Xiaoxin; Tang, Guoyi

    2015-03-01

    The effect of electropulsing ultrasonic shock (EUS) on the surface hardening and microstructure of Ti6Al4V alloy was studied. It was found that electropulsing improved the microhardness dramatically both in the influential depth and maximum value, compared with the only ultrasonic-shocked sample. It's indicated that refined surface layer with nanocrystalline and improved microhardness were obtained on account of surface severe plastic deformation, dynamic recrystallization (DRX) and phase change, which was implemented at relative low temperature and high strain rate/capacity due to the coupling of the thermal and athermal effects of EUS. It's different from conventional experiments and theory. It's discussed that the positive contributions of EPT in the thermodynamics and kinetics of microstructure and properties change were attributed to the reduction of nucleation energy barrier and acceleration of atomic diffusion. Therefore, it's supposed that EUS is an energy-saving and high-efficiency method of surface treatment technique with the help of high-energy electropulses, which is promising in cost reduction of the surface engineering and energy management. The work is supported by National Natural Science Foundation of China (No. 50571048) and Shenzhen science and technology research funding project of China (No. SGLH20121008144756946).

  13. Surface nanocrystalline and hardening effects of Ti-Al-V alloy by electropulsing ultrasonic shock

    NASA Astrophysics Data System (ADS)

    Ye, Xiaoxin

    2015-04-01

    The effect of electropulsing ultrasonic shock (EUS) on the surface hardening and microstructure of Ti6Al4V alloy was studied. It was found that electropulsing improved the microhardness dramatically both in the influential depth and maximum value, compared with the only ultrasonic-shocked sample. It's indicated that refined surface layer with nanocrystalline and improved microhardness were obtained on account of surface severe plastic deformation, dynamic recrystallization (DRX) and phase change, which was implemented at relative low temperature and high strain rate/capacity due to the coupling of the thermal and athermal effects of EUS. It's different from conventional experiments and theory. It's discussed that the positive contributions of EPT in the thermodynamics and kinetics of microstructure and properties change were attributed to the reduction of nucleation energy barrier and acceleration of atomic diffusion. Therefore, it's supposed that EUS is an energy-saving and high-efficiency method of surface treatment technique with the help of high-energy electropulses, which is promising in cost reduction of the surface engineering and energy management.

  14. Induced Anisotropy in FeCo-Based Nanocrystalline Ferromagnetic Alloys (HITPERM) by Very High Field Annealing

    NASA Technical Reports Server (NTRS)

    Johnson, F.; Garmestani, H.; Chu, S.-Y.; McHenry, M. E.; Laughlin, D. E.

    2004-01-01

    Very high magnetic field annealing is shown to affect the magnetic anisotropy in FeCo-base nanocrystalline soft ferromagnetic alloys. Alloys of composition Fe(44.5)Co(44.5)Zr(7)B(4) were prepared by melt spinning into amorphous ribbons, then wound to form toroidal bobbin cores. One set of cores was crystallized in a zero field at 600 deg. C for 1 h, then, field annealed at 17 tesla (T) at 480 deg. C for 1 h. Another set was crystallized in a 17-T field at 480 deg. C for 1 h. Field orientation was transverse to the magnetic path of the toroidal cores. An induced anisotropy is indicated by a sheared hysteresis loop. Sensitive torque magnetometry measurements with a Si cantilever sensor indicated a strong, uniaxial, longitudinal easy axis in the zero-field-crystallized sample. The source is most likely magnetoelastic anisotropy, caused by the residual stress from nanocrystallization and the nonzero magnetostriction coefficient for this material. The magnetostrictive coefficient lambda(5) is measured to be 36 ppm by a strain gage technique. Field annealing reduces the magnitude of the induced anisotropy. Core loss measurements were made in the zero-field-crystallized, zero-field-crystallized- than-field-annealed, and field-crystallized states. Core loss is reduced 30%-50% (depending on frequency) by field annealing. X-ray diffraction reveals no evidence of crystalline texture or orientation that would cause the induced anisotropy. Diffusional pair ordering is thought to be the cause of the induced anisotropy. However, reannealing the samples in the absence of a magnetic field at 480 deg. C does not completely remove the induced anisotropy.

  15. Predeformation and Subsequent Annealing—A Way for Controlling Morphology of Carbides in Large Dimensional Bulk Nanocrystalline Fe-Al-Cr Alloy

    NASA Astrophysics Data System (ADS)

    Wang, Hongding; La, Peiqing; Shi, Ting; Wei, Yupeng; Jiao, Huisheng

    2014-01-01

    In this study, a processing route is introduced to control the morphology of carbide and the grain size of nanocrystalline matrix of Fe-Al-Cr alloy. After predeformation followed by annealing treatment, the grain size of nanocrystalline matrix decreased slightly and the Cr7C3 phases transformed from a fiber shape to the globular shape. The yield strength and the flow stress of the alloy increased from 1048 to 1338 MPa and 1150 to 1550 MPa, respectively, while the ductility of the alloy also became better. This proposed method may open a way for controlling the morphology of carbide and the grain size of matrix in bulk nanocrystalline materials to receive higher strength and better plasticity.

  16. Growth in solution of hooked Ni-Fe fibers by oriented rotation and attachment approaches

    NASA Astrophysics Data System (ADS)

    Zhang, Yong; Liu, Fang; Zhang, Wei-ze

    2016-04-01

    Inspired by the curved branches of fractal trees, hooked Ni-Fe fibers were grown in situ in Ni-Fe composite coatings on a spheroidal graphite cast iron substrate. These hooked Ni-Fe fibers exhibited inclination angles of about 39°, which was in accordance with the theoretical prediction of 37°. Ni-Fe nanostructures self-assembled to form dendrites and evolved into hooked fibers by an oriented attachment reaction. The orientation rotation of Ni-Fe nanostructures played an important role in the growth of curved hooked Ni-Fe fibers. During sliding wear tests, the volume loss of the spheroidal graphite cast iron substrate was 2.2 times as large as that of the Ni-Fe coating reinforced by hooked fibers. The good load-transferring ability of hooked Ni-Fe fibers led to an improvement in their wear properties during wear tests.

  17. Structural, thermal, optical, and photoacoustic study of nanocrystalline Bi{sub 2}Te{sub 3} produced by mechanical alloying

    SciTech Connect

    Souza, S. M.; Triches, D. M.; Poffo, C. M.; Lima, J. C. de; Grandi, T. A.; Biasi, R. S. de

    2011-01-01

    Nanocrystalline Bi{sub 2}Te{sub 3} was produced by mechanical alloying and its properties were investigated by differential scanning calorimetry (DSC) x-ray diffraction (XRD), Raman spectroscopy (RS), and photoacoustic spectroscopy (PAS). Combining the XRD and RS results, the volume fraction of the interfacial component in as-milled and annealed samples was estimated. The PAS results suggest that the contribution of the interfacial component to the thermal diffusivity of nanostructured Bi{sub 2}Te{sub 3} is very significant.

  18. 90° magnetic coupling in a NiFe/FeMn/biased NiFe multilayer spin valve component investigated by polarized neutron reflectometry

    SciTech Connect

    Callori, S. J. Bertinshaw, J.; Cortie, D. L.; Cai, J. W. Zhu, T.; Le Brun, A. P.; Klose, F.

    2014-07-21

    We have observed 90° magnetic coupling in a NiFe/FeMn/biased NiFe multilayer system using polarized neutron reflectometry. Magnetometry results show magnetic switching for both the biased and free NiFe layers, the latter of which reverses at low applied fields. As these measurements are only capable of providing information about the total magnetization within a sample, polarized neutron reflectometry was used to investigate the reversal behavior of the NiFe layers individually. Both the non-spin-flip and spin-flip neutron reflectometry signals were tracked around the free NiFe layer hysteresis loop and were used to detail the evolution of the magnetization during reversal. At low magnetic fields near the free NiFe coercive field, a large spin-flip signal was observed, indicating magnetization aligned perpendicular to both the applied field and pinned layer.

  19. Control of gigahertz permeability and permittivity dispersion by means of nanocrystallization in FeCo based nanocrystalline alloy

    NASA Astrophysics Data System (ADS)

    Han, Mangui; Lu, Haipeng; Deng, Longjiang

    2010-11-01

    An amorphous (FeCo) based alloy has been prepared by a rapid quench method. Subsequent annealing on the amorphous samples gives rise to the coexistence of two magnetic phases: amorphous matrix and nanocrystalline grains (α'-FeCo) with an average size of 9.8 nm. Permeability dispersion behaviors have been studied by Kittel theory [C. Kittel, J. Phys. Radium 12, 332 (1951)]. The results show that these two magnetic phases contribute to the permeability dispersion. The Cole-Cole dispersion law [K. S. Cole and R. H. Cole, J. Chem. Phys. 9, 341 (1941)] has been employed to explain the permittivity dispersion within microwave region based on the assumption that multiple dielectric relaxation processes existing. Our results indicate the possibility of tuning the high frequency permeability and permittivity values of (FeCo) based alloy by controlling the magnetic microstructure, which suggests an alternative method to develop smart electromagnetic materials.

  20. Chemical synthesis, characterizations and magnetic properties of nanocrystalline Fe{sub 50}Co{sub 50} alloy

    SciTech Connect

    Dalavi, Shankar B.; Panda, Rabi Narayan; Raja, M. Manivel

    2014-04-24

    Nanocrystalline Fe{sub 50}Co{sub 50} alloy has been synthesized successfully by chemical reduction route using superhydride as reducing agent and oleic acid and oleylamine as capping agents. Phase purity, crystallite size and lattice parameters of the synthesized NPs are determined by X-ray powder diffraction method. FeCo alloy crystallizes in body centered cubic (bcc) structure having crystallite size equal to 29 nm and lattice parameters equal to 2.8546 Å. The size and shape morphologies of the material were studied by SEM analysis. SEM micrograph study shows the average particle size to be 60 nm and indicates the appearance of agglomerates of the nano-particles consisting of several crystallites. The room temperature magnetic hysteresis studies indicate ferromagnetic behavior of the materials. The values of saturation magnetization and coercivity were 65 emu/g and 460 Oe, respectively. Magnetic properties of the material were interpreted on the basis of fine particle magnetism.

  1. Structural and soft magnetic properties of a new nanocrystalline Fe-based and B-free alloy

    NASA Astrophysics Data System (ADS)

    Long, Jianguo; Laughlin, D. E.; McHenry, M. E.

    2008-04-01

    A new nanocrystalline Fe-based soft magnetic alloy is discussed here. Ingots of nanocrystalline alloys (FeCu)80ZrxSi20-x (x =5, 6, and 8) were prepared by arc melting. The ingots were remelted and cast into 25-30μm thick ribbons by a single roller melt spinning method. X-ray diffraction (XRD) revealed the as-spun ribbons to be amorphous. The structural evolution of these samples was studied by XRD and transmission electron microscopy (TEM) after annealing at 450, 480, and 550°C. XRD shows the primary nanocrystallization product to be the α-Fe(Si ) phase. The grain size was observed by TEM to be ˜10nm after annealing at 480°C for 1h and 14nm after 550°C for 1h. ac soft magnetic properties were measured using a Walker AMH 401 ac permeameter. The core loss at an exciting frequency f =100kHz and maximum induction Bm=1kG was determined to be less than 19W/kg.

  2. Dry etching of NiFe/Co and NiFe/Al-O/Co multilayers in an inductively coupled plasma of Cl{sub 2}/Ar mixture

    SciTech Connect

    Ra, H.-W.; Hahn, Y.B.; Song, K.S.; Park, M.H.; Hong, Y.K.

    2004-11-01

    Dry etching of NiFe/Co and NiFe/Al-O/Co multilayers was carried out in inductively coupled Cl{sub 2}/Ar plasmas. An ion-enhanced etch mechanism took a critical role for desorption of chlorine etch products. NiFe/Al-O/Co showed a faster etch rate than NiFe/Co at various etch conditions. Anisotropic and smooth features were obtained using a photoresist mask. Sidewall contamination with etch products was observed at a higher Cl{sub 2} concentration (>50%). Postetch cleaning of the etched samples in deionized water reduced the chlorine residues substantially.

  3. Exchange bias magnetism in films of NiFe/(Ni,Fe)O nanocrystallite dispersions

    SciTech Connect

    Hsiao, C.-H.; Chi, C.-C.; Wang, S.; Ouyang, H.; Desautels, R. D.; Lierop, J. van; Lin, K.-W.; Lin, T.-L.

    2014-05-07

    Ni{sub 3}Fe/(Ni,Fe)O thin films having a nanocrystallite dispersion morphology were prepared by a reactive ion beam-assisted deposition technique. The crystallite sizes of these dispersion-based films were observed to decrease from 8.4 ± 0.3 nm to 3.4 ± 0.3 nm as the deposition flow-rate increased from 2.78% to 7.89% O{sub 2}/Ar. Thin film composition was determined using selective area electron diffraction images and Multislice simulations. Through a detailed analysis of high resolution transmission electron microscopy images, the nanocrystallites were determined to be Ni{sub 3}Fe (a ferromagnet), NiO, and FeO (both antiferromagnets). It was determined that the interfacial molar Ni{sub 3}Fe ratio in the nanocrystallite dispersions increased slightly at first, then decreased as the oxygen content was increased; at 7.89% O{sub 2}/Ar, the interfacial molar ratio was essentially zero (only NiO and FeO remained). For nanocrystallite dispersion films grown with O{sub 2}/Ar flow-rate greater than 7.89%, no interfacial (intermixed) Ni{sub 3}Fe phase was detected, which resulted in no measurable exchange bias. Comparing the exchange bias field between the nanocrystallite dispersion films at 5 K, we observed a decrease in the magnitude of the exchange bias field as the nanocrystallite size decreased. The exchange bias coupling for all samples measured set in at essentially the same temperature (i.e., the exchange bias blocking temperature). Since the ferromagnetic/anti-ferromagnetic (FM/AFM) contact area in the nanocrystallite dispersion films increased as the nanocrystallite size decreased, the increase in the magnitude of the exchange bias could be attributed to larger regions of defects (vacancies and bond distortions) which occupied a significant portion of the FM/AFM interfaces in the nanocrystallite dispersion films.

  4. Multiphase and Double-Layer NiFe2O4@NiO-Hollow-Nanosphere-Decorated Reduced Graphene Oxide Composite Powders Prepared by Spray Pyrolysis Applying Nanoscale Kirkendall Diffusion.

    PubMed

    Park, Gi Dae; Cho, Jung Sang; Kang, Yun Chan

    2015-08-01

    Multicomponent metal oxide hollow-nanosphere decorated reduced graphene oxide (rGO) composite powders are prepared by spray pyrolysis with nanoscale Kirkendall diffusion. The double-layer NiFe2O4@NiO-hollow-nanosphere decorated rGO composite powders are prepared using the first target material. The NiFe-alloy-nanopowder decorated rGO powders are prepared as an intermediate product by post-treatment under the reducing atmosphere of the NiFe2O4/NiO-decorated rGO composite powders obtained by spray pyrolysis. The different diffusion rates of Ni (83 pm for Ni(2+)) and Fe (76 pm for Fe(2+), 65 pm for Fe(3+)) cations with different radii during nanoscale Kirkendall diffusion result in multiphase and double-layer NiFe2O4@NiO hollow nanospheres. The mean size of the hollow NiFe2O4@NiO nanospheres decorated uniformly within crumpled rGO is 14 nm. The first discharge capacities of the nanosphere-decorated rGO composite powders with filled NiFe2O4/NiO and hollow NiFe2O4@NiO at a current density of 1 A g(-1) are 1168 and 1319 mA h g(-1), respectively. Their discharge capacities for the 100th cycle are 597 and 951 mA h g(-1), respectively. The discharge capacity of the NiFe2O4@NiO-hollow-nanosphere-decorated rGO composite powders at the high current density of 4 A g(-1) for the 400th cycle is 789 mA h g(-1).

  5. RECENT PROGRESS IN THE DEVELOPMENT OF DUCTILE-PHASE TOUGHENED TUNGSTEN FOR PLASMA-FACING MATERIALS: W-Ni-Fe COMPOSITES

    SciTech Connect

    Henager, Charles H.; Stevens, Erica L.; Kurtz, Richard J.; Roosendaal, Timothy J.; Nyberg, Eric A.; Lavender, Curt A.; Odette, G Robert; Cunningham, Kevin; Zok, Frank W.

    2015-06-30

    A promising approach to increasing fracture toughness and decreasing the DBTT of a W-alloy is by ductile-phase toughening (DPT). In this method, a ductile phase is included in a brittle matrix to prevent fracture propagation by crack bridging or crack deflection. Liquid-phase sintered W-Ni-Fe alloys consisting of nearly spherical W-particles embedded within a Ni-Fe-W ductile matrix are being manipulated by hot-rolling to create lamellar W/Fe-Ni-W composites with anisotropic fracture properties. The rolled W-Ni-Fe alloy becomes a lamellar alloy consisting of W lamellae separated by ductile-phase regions. The W-rich lamellae are strong but brittle, while the ductile-phase metallic regions have a thin, plate-like morphology to provide a ductile bridging region. This rolled material is oriented with the W-rich lamellae parallel to principal stresses so that surface cracking is normal to the ductile-phase bridging regions.

  6. Morphology and magnetic behavior of cobalt rich amorphous/nanocrystalline (Co-Ni)70Ti10B20 alloyed powders

    NASA Astrophysics Data System (ADS)

    Raanaei, Hossein; Mohammad-Hosseini, Vahid

    2016-09-01

    The effect of milling time on microstructural and magnetic behavior of mechanically alloyed Co49Ni21Ti10B20 is investigated by using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, differential scanning calorimetry and vibrating sample magnetometer. It is shown, with increasing milling time, the crystallite size decreases and finally reaches to a low value after 190 h of milling time. The increase in microstrain is also observed during the milling process. The results indicate the coexistence between amorphous and nanocrystalline phases after 190 h of milling time. Moreover, the lowest magnetic coercivity of about 39 Oe at the final milling stage is observed. The results of annealed sample reveal structural ordering of constituent elements.

  7. Characterization of the NiFe sputter etch process in a rf plasma

    SciTech Connect

    Kropewnicki, Thomas J.; Paterson, Alex M.; Panagopoulos, Theodoros; Holland, John P.

    2006-05-15

    The sputter etching of NiFe thin films by Ar ions in a rf plasma has been studied and characterized with the use of a Langmuir probe. The NiFe sputter etch rate was found to depend strongly on incident ion energy, with the highest NiFe etch rates occurring at high rf bias power, low pressure, and moderate rf source power. NiFe etch rates initially increased with increasing rf source power, then saturated at higher rf source powers. Pressure had the weakest effect on NiFe etch rates. Empirically determined sputter yields based on the NiFe etch rates and ion current densities were calculated, and these compared favorably to sputter yields determined using the sputtering model proposed by Sigmund [Phys. Rev. 184, 383 (1969)].

  8. The Model [NiFe]-Hydrogenases of Escherichia coli.

    PubMed

    Sargent, F

    2016-01-01

    In Escherichia coli, hydrogen metabolism plays a prominent role in anaerobic physiology. The genome contains the capability to produce and assemble up to four [NiFe]-hydrogenases, each of which are known, or predicted, to contribute to different aspects of cellular metabolism. In recent years, there have been major advances in the understanding of the structure, function, and roles of the E. coli [NiFe]-hydrogenases. The membrane-bound, periplasmically oriented, respiratory Hyd-1 isoenzyme has become one of the most important paradigm systems for understanding an important class of oxygen-tolerant enzymes, as well as providing key information on the mechanism of hydrogen activation per se. The membrane-bound, periplasmically oriented, Hyd-2 isoenzyme has emerged as an unusual, bidirectional redox valve able to link hydrogen oxidation to quinone reduction during anaerobic respiration, or to allow disposal of excess reducing equivalents as hydrogen gas. The membrane-bound, cytoplasmically oriented, Hyd-3 isoenzyme is part of the formate hydrogenlyase complex, which acts to detoxify excess formic acid under anaerobic fermentative conditions and is geared towards hydrogen production under those conditions. Sequence identity between some Hyd-3 subunits and those of the respiratory NADH dehydrogenases has led to hypotheses that the activity of this isoenzyme may be tightly coupled to the formation of transmembrane ion gradients. Finally, the E. coli genome encodes a homologue of Hyd-3, termed Hyd-4, however strong evidence for a physiological role for E. coli Hyd-4 remains elusive. In this review, the versatile hydrogen metabolism of E. coli will be discussed and the roles and potential applications of the spectrum of different types of [NiFe]-hydrogenases available will be explored. PMID:27134027

  9. Interplay between out-of-plane anisotropic L11-type CoPt and in-plane anisotropic NiFe layers in CoPt/NiFe exchange springs

    NASA Astrophysics Data System (ADS)

    Saravanan, P.; Hsu, Jen-Hwa; Tsai, C. L.; Tsai, C. Y.; Lin, Y. H.; Kuo, C. Y.; Wu, J.-C.; Lee, C.-M.

    2014-06-01

    Films of L11-type CoPt/NiFe exchange springs were grown with different NiFe (Permalloy) layer thickness (tNiFe = 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 tNiFe and the perpendicular magnetic anisotropy of L11-type CoPt/NiFe films cannot sustain for tNiFe larger than 3.0 nm due to the existence of exchange interaction at the interface of L11-CoPt and NiFe layers. Magnetic force microscopy analysis on the as-grown samples shows the changes in morphology from maze-like domains with good contrast to hazy domains when tNiFe ≥ 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 tNiFe 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 tNiFe investigated. The results of present study demonstrate that the tunable tilted exchange springs can be realized with L11-type CoPt/NiFe bilayers for future applications in three-axis magnetic sensors or advanced spintronic devices demanding inclined magnetic anisotropy.

  10. Corrosion properties of electroplated CoNiFe films

    SciTech Connect

    Saito, M.; Yamada, K.; Ohashi, K.; Yasue, Y.; Sogawa, Y.; Osaka, T.

    1999-08-01

    Electroplated CoNiFe films with a saturation flux density as high as 2.1 T are potentially useful in high-density magnetic recording heads. The authors found that films electroplated at a high current density (15 mA/cm{sup 2}) from a bath without saccharin have a sufficient anodic pitting-corrosion potential ({minus}65 mV). The authors also found that the pitting-corrosion potential of films electroplated under a low current density (5 mA/cm{sup 2}) from saccharin-free baths have anodic pitting-corrosion potentials of less than {minus}300 mV. However, the corrosion resistance improved after annealing at temperatures above 100 C. The crystal-grain boundaries in the as-plated film that electroplated under a low current density from saccharin-free baths are not clear (i.e., that the phase is amorphous). But the crystal grain boundaries in the annealed film are clear. Films electroplated from baths containing saccharin also have anodic pitting-corrosion potentials of less than {minus}300 mV. Their corrosion resistance did not improve when they were annealed at 250 C. The deterioration of the corrosion resistance is attributed to the defects that increase the face-centered cubic (111) lattice constant. One of the most important characteristics of a highly corrosion-resistant CoNiFe film is fine crystal structure with very few defects.

  11. Magnetic characterization of nanocrystalline Fe80-xCrxCo20 (15≤x≤35) alloys during milling and subsequent annealing

    NASA Astrophysics Data System (ADS)

    Rastabi, Reza Amini; Ghasemi, Ali; Tavoosi, Majid; Sodaee, Tahmineh

    2016-10-01

    Magnetic characterization of nanocrystalline Fe-Cr-Co alloys during milling and annealing process was the goal of this study. To formation of Fe80-xCrxCo20 (15≤x≤35) solid solution, different powder mixtures of Fe, Cr and Co elements were mechanically milled in a planetary ball mill. The annealing process was done in as-milled samples at different temperature in the range of 500-640 °C for 2 h. The produced samples were characterized using X-ray diffraction, scanning electron microscopy, differential scanning calorimetry and vibrating sample magnetometer. Performed mechanical alloying in different powder mixtures lead to the formation of Fe-Cr-Co α-phase solid solution with average crystallite sizes of about 10 nm. The produced nanocrystalline alloys exhibit magnetic properties with the coercivity and saturation of magnetization in the range of 110-200 Oe and 150-220 emu/g, respectively. The coercivity of produced alloys after annealing process decreased and reached to about 40-150 Oe. The highest value of coercivity in as-milled and annealed samples was achieved in alloys with higher Cr contents.

  12. Molecular evolution of gas cavity in [NiFeSe] hydrogenases resurrected in silico.

    PubMed

    Tamura, Takashi; Tsunekawa, Naoki; Nemoto, Michiko; Inagaki, Kenji; Hirano, Toshiyuki; Sato, Fumitoshi

    2016-01-01

    Oxygen tolerance of selenium-containing [NiFeSe] hydrogenases (Hases) is attributable to the high reducing power of the selenocysteine residue, which sustains the bimetallic Ni-Fe catalytic center in the large subunit. Genes encoding [NiFeSe] Hases are inherited by few sulphate-reducing δ-proteobacteria globally distributed under various anoxic conditions. Ancestral sequences of [NiFeSe] Hases were elucidated and their three-dimensional structures were recreated in silico using homology modelling and molecular dynamic simulation, which suggested that deep gas channels gradually developed in [NiFeSe] Hases under absolute anaerobic conditions, whereas the enzyme remained as a sealed edifice under environmental conditions of a higher oxygen exposure risk. The development of a gas cavity appears to be driven by non-synonymous mutations, which cause subtle conformational changes locally and distantly, even including highly conserved sequence regions. PMID:26818780

  13. Molecular evolution of gas cavity in [NiFeSe] hydrogenases resurrected in silico

    NASA Astrophysics Data System (ADS)

    Tamura, Takashi; Tsunekawa, Naoki; Nemoto, Michiko; Inagaki, Kenji; Hirano, Toshiyuki; Sato, Fumitoshi

    2016-01-01

    Oxygen tolerance of selenium-containing [NiFeSe] hydrogenases (Hases) is attributable to the high reducing power of the selenocysteine residue, which sustains the bimetallic Ni-Fe catalytic center in the large subunit. Genes encoding [NiFeSe] Hases are inherited by few sulphate-reducing δ-proteobacteria globally distributed under various anoxic conditions. Ancestral sequences of [NiFeSe] Hases were elucidated and their three-dimensional structures were recreated in silico using homology modelling and molecular dynamic simulation, which suggested that deep gas channels gradually developed in [NiFeSe] Hases under absolute anaerobic conditions, whereas the enzyme remained as a sealed edifice under environmental conditions of a higher oxygen exposure risk. The development of a gas cavity appears to be driven by non-synonymous mutations, which cause subtle conformational changes locally and distantly, even including highly conserved sequence regions.

  14. Influence of quenching rate on the magnetic and martensitic properties of Ni-Fe-Ga melt-spun ribbons

    SciTech Connect

    Okumura, H.; Uemura, K.

    2010-08-15

    We have fabricated Ni-Fe-Ga {beta} single phase alloy ribbons with Ga content less than 25 at. %. Higher spinning rate of melt-spinning technique can produce {beta} single phase alloys without precipitation of {gamma} particles, whereas lower spinning rate results in the {beta}+{gamma} two phase structure. This higher quenching rate is found to be able to fully suppress the formation of {gamma} phase during fabrication. The martensitic and magnetic transition temperatures of {beta} phase ribbons are both above room temperature, and the ribbon show saturation magnetization as high as 56.5 emu/g at room temperature. These features are attractive for practical applications. The effects of quenching rate on microstructure, martensitic transformation, and magnetic properties are discussed.

  15. A highly active and coke-resistant steam reforming catalyst comprising uniform nickel-iron alloy nanoparticles.

    PubMed

    Koike, Mitsuru; Li, Dalin; Nakagawa, Yoshinao; Tomishige, Keiichi

    2012-12-01

    Doing fine with Ni-Fe: The calcination and reduction of a hydrotalcite precursor containing Ni and Fe ions gives uniform Ni-Fe alloy nanoparticles mixed with Mg(Ni, Fe, Al)O particles. The uniformity of the Ni-Fe alloy nanoparticles is connected to the catalyst's high activity and resistance to coke formation in toluene and phenol steam reforming reactions.

  16. RECENT PROGRESS IN THE DEVELOPMENT OF DUCTILE-PHASE TOUGHENED TUNGSTEN FOR PLASMA-FACING MATERIALS: W-Ni-Fe COMPOSITES

    SciTech Connect

    Henager, Charles H.; Kurtz, Richard J.; Roosendaal, Timothy J.; Borlaug, Brennan A.; Nyberg, Eric A.; Lavender, Curt A.; Odette, G Robert; Cunningham, Kevin; Zok, Frank W.

    2015-03-02

    A promising approach to increasing fracture toughness and decreasing the DBTT of a W-alloy is by ductile-phase toughening (DPT) [1-3]. In this method, a ductile phase is included in a brittle matrix to prevent fracture propagation by crack bridging. W-Ni-Fe alloys consisting of nearly spherical W-particles embedded within a Fe-Ni-W ductile matrix are being manipulated by hot-rolling to create lamellar W/Fe-Ni-W composites with anisotropic fracture properties.

  17. Voltammetric behavior of tiopronin on carbon paste electrode modified with nanocrystalline Fe₅₀Ni₅₀ alloys.

    PubMed

    Baghayeri, Mehdi; Maleki, Behrooz; Zarghani, Rahele

    2014-11-01

    A simple and sensitive sensor was proposed for the rapid determination of tiopronin (TP) using a carbon paste electrode (CPE) modified with synthesized nanocrystalline Ni50-Fe50 alloys (nano-Ni50-Fe50) and ferrocene carboxylic acid (FcCa). The synthesized nano-Ni50-Fe50 was characterized by different methods such as TEM, SEM and XRD. The electrochemical oxidation of TP on the nano-Ni50-Fe50/FcCa carbon paste electrode (nano-Ni50-Fe50/FcCa/CPE) was studied. The nano-Ni50-Fe50/FcCa/CPE exhibited good electrocatalytic properties towards oxidation of TP in phosphate buffer solution (pH7.0) with an overpotential of about 500 mV lower than that of the bare electrode. The rate constant for the catalytic oxidation of TP was evaluated by rotating disk voltammetry and the value of kc was found to be 3.2 × 10(7) cm(3)mol(-1)s(-1). Using differential pulse voltammetry (DPV), the determination of TP was explored at the modified electrode. The results indicated that the differential pulse response of TP was linear with its concentration in the range of 0.01-50.0 μM. The detection limit was 7.46 nM (S/N=3). The proposed sensor was successfully applied for the determination of TP in tablet and urine samples.

  18. Effects of peak current density on the mechanical properties of nanocrystalline Ni Co alloys produced by pulse electrodeposition

    NASA Astrophysics Data System (ADS)

    Li, Yundong; Jiang, Hui; Huang, Weihua; Tian, Hui

    2008-08-01

    Cobalt content, grain size, microhardness and tensile strength of nanocrystalline Ni-Co deposits produced from a solution containing saccharin and cobalt sulfate at constant electrodeposition conditions (pulse on-time Ton at 1 ms and pulse off-time Toff at 15 ms) but varying the peak current density Jp were investigated. It is found that an increase in Jp makes the deposit Co content lower, colony-like morphology more obvious, grain size smaller, and hardness and tensile strength higher. All of the facts are believed to result from the higher overpotential and nucleation rates caused by the Jp increase. But its further increase could lead to reduction in the hardness and tensile strength. Peak current densities in the range of 100-120 A dm -2 are recommended for the preparation of nanostructured Ni-Co alloy deposits with grain sizes in the range of 15-20 nm, containing 7-8% Co, possessing hardness of 590-600 kg mm -2 and tensile strength of 1180-1200 MPa—significantly higher than the strength of pure nickel deposit which is produced by the similar method and gets similar grain size.

  19. Synthesis, characterization and low temperature electrical conductivity of Polyaniline/NiFe2O4 nanocomposites

    NASA Astrophysics Data System (ADS)

    Prasanna, G. D.; Prasad, V. B.; Jayanna, H. S.

    2015-02-01

    Conducting polymer/ferrite nanocomposites with an organized structure provide a new functional hybrid between organic and inorganic materials. The most popular among the conductive polymers is the polyaniline (PANI) due to its wide application in different fields. In the present work nickel ferrite (NiFe2O4) nanoparticles were prepared by sol-gel citrate-nitrate method with an average size of 21.6nm. PANI/NiFe2O4 nanoparticles were synthesized by a simple general and inexpensive in-situ polymerization in the presence of NiFe2O4 nanoparticles. The effects of NiFe2O4 nanoparticles on the dc-electrical properties of polyaniline were investigated. The structural components in the nanocomposites were identified from Fourier Transform Infrared (FTIR) spectroscopy. The crystalline phase of nanocomposites was characterized by X-Ray Diffraction (XRD). The Scanning Electron Micrograph (SEM) reveals that there was some interaction between the NiFe2O4 particles and polyaniline and the nanocomposites are composed of polycrystalline ferrite nanoparticles and PANI. The dc conductivity of polyaniline/NiFe2O4 nanocomposites have been measured as a function of temperature in the range of 80K to 300K. It is observed that the room temperature conductivity cRT decreases with increase in the relative content of NiFe2O4. The experimental data reveals that the resistivity increases for all composites with decrease of temperature exhibiting semiconductor behaviour.

  20. Lattice dynamics and thermoelectric properties of nanocrystalline silicon-germanium alloys

    SciTech Connect

    Claudio, Tania; Stein, Niklas; Peterman, Nils; Stroppa, Daniel; Koza, Michael M.; Wiggers, Hartmut; Klobes, B.; Schierning, Gabi; Hermann, Raphael P.

    2015-10-26

    The lattice dynamics and thermoelectric properties of sintered phosphorus-doped nanostructured silicon- germanium alloys obtained by gas-phase synthesis were studied. Measurements of the density of phonon states by inelastic neutron scattering were combined with measurements of the elastic constants and the low- temperature heat capacity. A strong influence of nanostructuring and alloying on the lattice dynamics was observed. The thermoelectric transport properties of samples with different doping as well as samples sintered at different temperature were characterized between room temperature and 1000C. A peak figure of merit zT = 0:88 at 900C is observed and comparatively insensitive to the aforementioned param- eter variations.

  1. Hydrogen Storage Characteristics of Nanocrystalline and Amorphous Nd-Mg-Ni-Based NdMg12-Type Alloys Synthesized via Mechanical Milling

    NASA Astrophysics Data System (ADS)

    Zhang, Yanghuan; Shang, Hongwei; Hou, Zhonghui; Yuan, Zeming; Yang, Tai; Qi, Yan

    2016-09-01

    In this study, Mg was partially substituted by Ni with the intent of improving the hydrogen storage kinetics performance of NdMg12-type alloy. Mechanical milling technology was adopted to fabricate the nanocrystalline and amorphous NdMg11Ni + x wt pct Ni (x = 100, 200) alloys. The effects of Ni content and milling duration on the microstructures and hydrogen storage kinetics of as-milled alloys have been systematically investigated. The structures were characterized by XRD and HRTEM. The electrochemical hydrogen storage properties were tested by an automatic galvanostatic system. Moreover, the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter connected with a H2 detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. The results reveal that the increase of Ni content dramatically ameliorates the gaseous and electrochemical hydrogen storage kinetics performance of the as-milled alloys. Furthermore, high rate discharge ability (HRD) reach the maximum value with the variation of milling time. The maximum HRDs of the NdMg11Ni + x wt pct Ni (x = 100, 200) alloys are 80.24 and 85.17 pct. The improved gaseous hydrogen storage kinetics of alloys via increasing Ni content and milling time can be attributed to a decrease in the hydrogen desorption activation energy.

  2. Magnetic field driving gradient effects on the microstructure in amorphous-nanocrystalline cobalt alloy ribbons

    NASA Astrophysics Data System (ADS)

    Tang, Zhaowei; Song, Yujun; Sun, Qiangqiang; Zhang, Tao; Jiang, Yanwei

    2012-01-01

    Field effects on the early crystallization of Co-rich amorphous ribbons (Co68.15Fe4.35Si12.5B15, atomic%) performed at 450 °C for 30 minutes in an applied 10 Oe longitudinal or transverse external magnetic field are investigated by comparing with the as-spun and annealed samples in zero applied magnetic field. Results indicate that the crystallization on the surface skin of the ribbon differs from that of the middle section due to the combined effects from the field direction and the defects or stress characteristics across the ribbons. In particular, the ribbons annealed under a transverse field exhibit an extremely distinct graded microstructure across the ribbon, which features amorphous-phased skin layers (top and bottom) of about 4-5 μm thickness and a middle amorphous-nanocrystalline composite layer about 10-12 μm thick, with the nanograins of 434 +/- 99 nm dispersing in the amorphous matrix.Field effects on the early crystallization of Co-rich amorphous ribbons (Co68.15Fe4.35Si12.5B15, atomic%) performed at 450 °C for 30 minutes in an applied 10 Oe longitudinal or transverse external magnetic field are investigated by comparing with the as-spun and annealed samples in zero applied magnetic field. Results indicate that the crystallization on the surface skin of the ribbon differs from that of the middle section due to the combined effects from the field direction and the defects or stress characteristics across the ribbons. In particular, the ribbons annealed under a transverse field exhibit an extremely distinct graded microstructure across the ribbon, which features amorphous-phased skin layers (top and bottom) of about 4-5 μm thickness and a middle amorphous-nanocrystalline composite layer about 10-12 μm thick, with the nanograins of 434 +/- 99 nm dispersing in the amorphous matrix. Electronic supplementary information (ESI) available. See DOI: 10.1039/c1nr10968e

  3. Electrochemical Evaluation of Nanocrystalline Diamond Thin Films on Ti-6Al-4V Implant Alloy

    NASA Astrophysics Data System (ADS)

    Fries, Marc; Venugopalan, Ramakrishna; Vohra, Yogesh

    2002-03-01

    Some 186,000 hip replacement surgeries are peformed every year in the United States alone. About 10surgeries are revision operations to replace an implant that has most likely failed through mechanical-electrochemical interactions resulting in implant wear. The ability to enhance the resistance to such mechanical-electrochemical interaction and thereby reduce wear could result in significantly increased device lifespan. Nanocrystalline diamond (NCD) thin films were deposited on Ti-6Al-4V disk samples (processed per ASTM F86 standard for medical implant surface conditions) using microwave plasma chemical vapor deposition (MPCVD). As a first step, these samples (n=3/test per group) were subjected to electrochemical evaluation in inorganic neutral salt solution at 37 C. The electrochemical evaluation involved both impedence spectroscopy (per ASTM G106) and polarization testing (per ASTM G5). The impedence spectroscopy data indicated a significantly higher charge transfer resistance at the interface due to the protective NCD as compared to the bare or uncoated substrate. The polarization test data confirmed that this increased charge transfer resistance resulted in a decreased current density measurement. This decreased current density measurement resulted in an order of magnitude lower calculated static corrosion rate from the NCD coated samples as opposed to the uncoated controls. Future studies will focus on investigations that will facilitate transfer of these static electrochemical resistance results to a more relevant mechanical-electrochemical interaction milieu.

  4. Influence of microstructure on soft magnetic properties of low coreloss and high Bs Fe85Si2B8P4Cu1 nanocrystalline alloy

    NASA Astrophysics Data System (ADS)

    Sharma, Parmanand; Zhang, Xin; Zhang, Yan; Makino, Akihiro

    2014-05-01

    Microstructure and magnetic properties of high Bs Fe85Si2B8P4Cu1 nano-crystalline alloy were tailored. The Bs ˜ 1.85 T and low coercivity Hc ˜ 6 A/m were obtained by conventional annealing (i.e., one step) at a heating rate of ˜400 °C/min. While one step annealing process produces a fairly stable nanostructure, for short times at temperatures <425 °C, the nanostructure and concomitant magnetic properties of this alloy are shown to be tunable by two step annealing process. Nanocrystalline ribbons with grain size (D) ranging from ˜15 to 32 nm, Hc ˜ 6 to 140 A/m and core-loss at 1.5 T, 50 Hz ˜ 0.39 ˜ 5.0 W/kg were obtained. The Hc of Fe85Si2B8P4Cu1 alloy is shown to vary as D6, but a small deviation was noticed, which may be due to weak anisotropy.

  5. Lattice dynamics and thermoelectric properties of nanocrystalline silicon-germanium alloys

    DOE PAGESBeta

    Claudio, Tania; Stein, Niklas; Peterman, Nils; Stroppa, Daniel; Koza, Michael M.; Wiggers, Hartmut; Klobes, B.; Schierning, Gabi; Hermann, Raphael P.

    2015-10-26

    The lattice dynamics and thermoelectric properties of sintered phosphorus-doped nanostructured silicon- germanium alloys obtained by gas-phase synthesis were studied. Measurements of the density of phonon states by inelastic neutron scattering were combined with measurements of the elastic constants and the low- temperature heat capacity. A strong influence of nanostructuring and alloying on the lattice dynamics was observed. The thermoelectric transport properties of samples with different doping as well as samples sintered at different temperature were characterized between room temperature and 1000C. A peak figure of merit zT = 0:88 at 900C is observed and comparatively insensitive to the aforementioned param-more » eter variations.« less

  6. Novel Nanocrystalline Intermetallic Coatings for Metal Alloys in Coal-fired Environments

    SciTech Connect

    Z. Zak Fang; H. Y. Sohn

    2009-08-31

    Intermetallic coatings (iron aluminide and nickel aluminide) were prepared by a novel reaction process. In the process, the aluminide coating is formed by an in-situ reaction between the aluminum powder fed through a plasma transferred arc (PTA) torch and the metal substrate (steel or Ni-base alloy). Subjected to the high temperature within an argon plasma zone, aluminum powder and the surface of the substrate melt and react to form the aluminide coatings. The prepared coatings were found to be aluminide phases that are porosity-free and metallurgically bonded to the substrate. The coatings also exhibit excellent high-temperature corrosion resistance under the conditions which simulate the steam-side and fire-side environments in coal-fired boilers. It is expected that the principle demonstrated in this process can be applied to the preparation of other intermetallic and alloy coatings.

  7. A lifetime-prediction approach to understanding corrosion: The corrosion-fatigue and corrosion behavior of a nickel-based superalloy and a nanocrystalline alloy

    NASA Astrophysics Data System (ADS)

    Steward, Rejanah Vernice

    Lifetime-prediction models are useful for simulating a material's in-service behavior or outcome. Perhaps the greatest advantage of these models is the ability to use the predicted results to help optimize engineering designs and reduce costs. The HastelloyRTM C-2000RTM superalloy is a single-phase material and face-centered cubic in structure at all temperatures. The C-2000RTM alloy is a commercially designed alloy manufactured to function in both reducing and oxidizing solutions. C-2000RTM is used as a fabrication material for heat exchangers, piping for chemical refineries, and storage repositories. The corrosion properties of C-2000RTM are excellent, and the ductility and fatigue properties are good. In this study, C-2000RTM is used to verify the theoretical basis of an electrochemical-micromechanical crack-initiation corrosion-fatigue model for materials under passive electrochemical conditions. The results from electrochemical and mechanical experiments, along with the findings from the conventional electron microscopy and a laser interferometer will be presented. A nanocrystalline Ni-18 weight percent (wt.%) Fe alloy is examined to investigate its electrochemical behavior in a 3.5 wt.% NaCl solution. Three Ni-18 wt.% Fe samples were annealed at 400°C for 3, 8, and 24 hours (hrs.) to study the effects of grain sizes on the electrochemical properties of bulk Ni-18 wt.% Fe. The electrochemical results from the annealed samples are compared with those measured for the as-received Ni-18 wt.% Fe material consisting of an average grain size of 23 nanometers (nm). The samples annealed for times longer than 8 hrs. appear to have undergone an abnormal grain growth, where nanometer and micrometer (mum) grain sizes are present. Unlike the electrochemical results for the as-received material, the annealed nanocrystalline materials appear to be susceptible to localized corrosion. Consequently, these larger grains within the nanoncrystalline-grain matrix are

  8. Magnetic properties of NiFe2O4/carbon nanofibers from Venezuelan petcoke

    NASA Astrophysics Data System (ADS)

    Briceño, Sarah; Silva, Pedro; Molina, Wilmer; Brämer-Escamilla, Werner; Alcalá, Olgi; Cañizales, Edgard

    2015-05-01

    NiFe2O4/carbon nanofibers (NiFe2O4/CNFs) have been successfully synthesized by hydrotermal method using Venezuelan petroleum coke (petcoke) as carbon source and NiFe2O4 as catalyst. The morphology, structural and magnetic properties of nanocomposite products were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), vibrating sample magnetometry (VSM) and electron paramagnetic resonance (EPR). XRD analysis revealed a cubic spinel structure and ferrite phase with high crystallinity. HR-TEM reveals the presence of CNFs with diameters of 4±2 nm. At room temperature, NiFe2O4/CNFs show superparamagnetic behavior with a maximum magnetization of 15.35 emu/g. Our findings indicate that Venezuelan petroleum coke is suitable industrial carbon source for the growth of magnetic CNFs.

  9. Molecular evolution of gas cavity in [NiFeSe] hydrogenases resurrected in silico

    PubMed Central

    Tamura, Takashi; Tsunekawa, Naoki; Nemoto, Michiko; Inagaki, Kenji; Hirano, Toshiyuki; Sato, Fumitoshi

    2016-01-01

    Oxygen tolerance of selenium-containing [NiFeSe] hydrogenases (Hases) is attributable to the high reducing power of the selenocysteine residue, which sustains the bimetallic Ni–Fe catalytic center in the large subunit. Genes encoding [NiFeSe] Hases are inherited by few sulphate-reducing δ-proteobacteria globally distributed under various anoxic conditions. Ancestral sequences of [NiFeSe] Hases were elucidated and their three-dimensional structures were recreated in silico using homology modelling and molecular dynamic simulation, which suggested that deep gas channels gradually developed in [NiFeSe] Hases under absolute anaerobic conditions, whereas the enzyme remained as a sealed edifice under environmental conditions of a higher oxygen exposure risk. The development of a gas cavity appears to be driven by non-synonymous mutations, which cause subtle conformational changes locally and distantly, even including highly conserved sequence regions. PMID:26818780

  10. Mechanisms of Formation and Transformation of Ni-Fe Hydroxycarbonates

    SciTech Connect

    Refait, Ph.; Jeannin, M.; Reffass, M.; Drissi, S.H.; Abdelmoula, M.; Genin, J.-M.R.

    2005-04-26

    The mechanisms of the transformation of (Ni,Fe)(OH)2 precipitates in carbonated aqueous solutions were studied. The reactions were monitored by measuring the redox potential of the aqueous suspension, and end products were studied by Moessbauer spectroscopy, X-ray diffraction and Raman spectroscopy. The oxidation processes were compared to those occurring without Ni, that is when the initial hydroxide is Fe(OH)2. Schematically, the oxidation of Fe(OH)2 involves two intermediate compounds, the carbonated GR of formula Fe{sup II}{sub 4}Fe{sup III}{sub 2}(OH){sub 12}CO{sub 3} {center_dot} 2H{sub 2}O, and ferrihydrite, before to lead finally to goethite {alpha}-FeOOH. It proved possible to prepare Ni(II)-Fe(III) hydroxycarbonates with ratios Fe/Ni from 1/6 to 1/3. When the Fe/Ni ratio is larger than 1/3, a two stage oxidation process takes place. The first stage leads to a Ni(II)-Fe(II)-Fe(III) hydroxycarbonate. The second stage corresponds to the oxidation of the Fe(II) remaining inside the hydroxycarbonate and leads to a mixture of Ni(II)-Fe(III) hydroxycarbonate with ferrihydrite. The main effect of Ni is then to stop the reaction at an intermediate stage, as Ni(II) is not oxidised by O2, leaving unchanged the main features of the mechanisms of transformation.

  11. Unusual reaction of [NiFe]-hydrogenases with cyanide.

    PubMed

    Hexter, Suzannah V; Chung, Min-Wen; Vincent, Kylie A; Armstrong, Fraser A

    2014-07-23

    Cyanide reacts rapidly with [NiFe]-hydrogenases (hydrogenase-1 and hydrogenase-2 from Escherichia coli) under mild oxidizing conditions, inhibiting the electrocatalytic oxidation of hydrogen as recorded by protein film electrochemistry. Electrochemical, EPR, and FTIR measurements show that the final enzyme product, formed within a second (even under 100% H2), is the resting state known as Ni-B, which contains a hydroxido-bridged species, Ni(III)-μ(OH)-Fe(II), at the active site. "Cyanide inhibition" is easily reversed because it is simply the reductive activation of Ni-B. This paper brings back into focus an observation originally made in the 1940s that cyanide inhibits microbial H2 oxidation and addresses the interesting mechanism by which cyanide promotes the formation of Ni-B. As a much stronger nucleophile than hydroxide, cyanide binds more rapidly and promotes oxidation of Ni(II) to Ni(III); however, it is quickly replaced by hydroxide which is a far superior bridging ligand.

  12. One-Pot Synthesis of (NiFe2O4)x-(SrFe12O19)1-x Nanocomposites and Their Microwave Absorption Properties.

    PubMed

    Hazra, Subhenjit; Ghosh, Barun Kumar; Patra, Manoj Kumar; Jani, Raj Kumar; Vadera, Sampat Raj; Ghosh, Narendra Nath

    2015-09-01

    In this paper, we report a simple but novel aqueous solution based 'one-pot' method for preparation of (NiFe2O4)x-(SrFe12O19)1-x nanocomposites consist of hard ferrite-soft ferrite phases. A physical mixing method has also been employed to prepare nanocomposites having same compositions. The effects of synthetic methodologies on the microstructures of the nanocomposites as well as their magnetic and microwave absorption properties have been evaluated. Crystal structures and microstructures of these composites have been investigated by using X-ray diffraction, transmission electron microscope and scanning electron microscope. In the nanocomposites, prepared by both methods, presence of nanocrystalline NiFe2O4 and SrFe12O19 phases was detected. However, nanocomposites, prepared by one-pot method, possessed better homogeneous distribution of hard and soft ferrite phases than the nanocomposites, prepared by physical mixing method. Nanocomposites, prepared by one-pot method, demonstrated significant spring exchange coupling interaction between hard and soft ferrite phases and exhibited magnetically single phase behaviour. The spring exchange coupling interaction enhanced the magnetic properties (high saturation magnetization and coercivity) and microwave absorption properties of the nanocomposites, prepared by one-pot method, in comparison with the nanocomposites prepared by physical mixing method as well as pure NiFe2O4 and SrFe12O19 nanoparticles. Minimum reflection loss of the composite was ~ -17 dB (i.e., 98% absorption) at 8.2 GHz for an absorber thickness of 3.2 mm.

  13. One-Pot Synthesis of (NiFe2O4)x-(SrFe12O19)1-x Nanocomposites and Their Microwave Absorption Properties.

    PubMed

    Hazra, Subhenjit; Ghosh, Barun Kumar; Patra, Manoj Kumar; Jani, Raj Kumar; Vadera, Sampat Raj; Ghosh, Narendra Nath

    2015-09-01

    In this paper, we report a simple but novel aqueous solution based 'one-pot' method for preparation of (NiFe2O4)x-(SrFe12O19)1-x nanocomposites consist of hard ferrite-soft ferrite phases. A physical mixing method has also been employed to prepare nanocomposites having same compositions. The effects of synthetic methodologies on the microstructures of the nanocomposites as well as their magnetic and microwave absorption properties have been evaluated. Crystal structures and microstructures of these composites have been investigated by using X-ray diffraction, transmission electron microscope and scanning electron microscope. In the nanocomposites, prepared by both methods, presence of nanocrystalline NiFe2O4 and SrFe12O19 phases was detected. However, nanocomposites, prepared by one-pot method, possessed better homogeneous distribution of hard and soft ferrite phases than the nanocomposites, prepared by physical mixing method. Nanocomposites, prepared by one-pot method, demonstrated significant spring exchange coupling interaction between hard and soft ferrite phases and exhibited magnetically single phase behaviour. The spring exchange coupling interaction enhanced the magnetic properties (high saturation magnetization and coercivity) and microwave absorption properties of the nanocomposites, prepared by one-pot method, in comparison with the nanocomposites prepared by physical mixing method as well as pure NiFe2O4 and SrFe12O19 nanoparticles. Minimum reflection loss of the composite was ~ -17 dB (i.e., 98% absorption) at 8.2 GHz for an absorber thickness of 3.2 mm. PMID:26716212

  14. Deposition of NiFe(200) and NiFe(111) textured films onto Si/SiO2 substrates by DC magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Dzhumaliev, A. S.; Nikulin, Yu. V.; Filimonov, Yu. A.

    2016-05-01

    The effect of substrate temperature T sub and bias voltage U bias on the texture of NiFe films with thickness d ˜ 30-340 nm deposited by DC magnetron sputtering onto Si(111)/SiO2 substrates under working gas pressure ˜ 0.2 Pa has been investigated. It has been demonstrated that films grown at room substrate temperature have the (111) texture that is refined under a negative bias voltage. The deposition of films onto a grounded ( U bias ˜ 0) substrate heated to T sub ˜ 440-640 K results in the formation of textured NiFe(200) films.

  15. Self-biased magnetoelectric coupling characteristics of three-phase composite transducers with nanocrystallin soft magnetic alloy

    NASA Astrophysics Data System (ADS)

    Huang, Dongyan; Lu, Caijiang; Bing, Han

    2015-07-01

    This paper reports the self-biased magnetoelectric (ME) effects in composites consisting of high-permeability Fe-based nanocrystalline soft magnetic alloy Fe73.5Cu1Nb3Si13.5B9 (FeCuNbSiB), pure nickel (Ni) and piezoelectric lead zirconate titanate (PZT). The FeCuNbSiB ribbons are fabricated on traditional laminates Ni/PZT/Ni through two modes: the attached mode (F-NPN-F) and the laminated mode (F/NPN/F). The F-NPN-F composite sufficiently reveals that the high-permeability FeCuNbSiB ribbons concentrate more magnetic flux in magnetostrictive Ni, which results in the self-biased ME effects of F-NPN-F. For the F/NPN/F composite, the FeCuNbSiB acts as the dynamic driver to enhance the effective piezomagnetic coefficient of Ni. The giant self-biased ME effects of F/NPN/F are because of the internal magnetic field between Ni and FeCuNbSiB due to their different magnetic characteristics. The influences of the numbers of FeCuNbSiB layers ( L) on the resonant ME voltage coefficients ( α ME ,r ) for F-NPN-F and F/NPN/F composites are investigated in detail. The experiments demonstrate that the maximum α ME ,r at zero-biased field is 80 V/cm Oe for F-NPN-F with L = 2, and 85 V/cm Oe for F/NPN/F with L = 4. This paper demonstrates that these two ME composites are suitable for achieving zero-biased ME transducers, power-free magnetic field sensors and energy harvesters.

  16. 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

  17. Force Field Development and Molecular Dynamics of [NiFe] Hydrogenase

    SciTech Connect

    Smith, Dayle MA; Xiong, Yijia; Straatsma, TP; Rosso, Kevin M.; Squier, Thomas C.

    2012-05-09

    Classical molecular force-field parameters describing the structure and motion of metal clusters in [NiFe] hydrogenase enzymes can be used to compare the dynamics and thermodynamics of [NiFe] under different oxidation, protonation, and ligation circumstances. Using density functional theory (DFT) calculations of small model clusters representative of the active site and the proximal, medial, and distal Fe/S metal centers and their attached protein side chains, we have calculated classical force-field parameters for [NiFe] in reduced and oxidized states, including internal coordinates, force constants, and atom-centered charges. Derived force constants revealed that cysteinate ligands bound to the metal ions are more flexible in the Ni-B active site, which has a bridging hydroxide ligand, than in the Ni-C active site, which has a bridging hydride. Ten nanosecond all-atom, explicit-solvent MD simulations of [NiFe] hydrogenase in oxidized and reduced catalytic states established the stability of the derived force-field parameters in terms of C{alpha} and metal cluster fluctuations. Average active site structures from the protein MD simulations are consistent with [NiFe] structures from the Protein Data Bank, suggesting that the derived force-field parameters are transferrable to other hydrogenases beyond the structure used for testing. A comparison of experimental H{sub 2}-production rates demonstrated a relationship between cysteinate side chain rotation and activity, justifying the use of a fully dynamic model of [NiFe] metal cluster motion.

  18. Structural, thermal, and photoacoustic study of nanocrystalline Cr{sub 3}Ge produced by mechanical alloying

    SciTech Connect

    Prates, P. B.; Maliska, A. M.; Ferreira, A. S.; Borges, Z. V.; Lima, J. C. de

    2015-10-21

    A thermodynamic analysis of the Cr-Ge system suggested that it was possible to produce a nanostructured Cr{sub 3}Ge phase by mechanical alloying. The same analysis showed that, due to low activation energies, Cr-poor crystalline and/or amorphous alloy could also be formed. In fact, when the experiment was performed, Cr{sub 11}Ge{sub 19} and amorphous phases were present for small milling times. For milling times larger than 15 h these additional phases decomposed and only the nanostructured Cr{sub 3}Ge phase remained up to the highest milling time used (32 h). From the differential scanning calorimetry measurements, the Avrami exponent n was obtained, indicating that the nucleation and growth of the nanostructured Cr{sub 3}Ge phase may be restricted to one or two dimensions, where the Cr and Ge atoms diffuse along the surface and grain boundaries. In addition, contributions from three-dimensional diffusion with a constant nucleation rate may be present. The thermal diffusivity of the nanostructured Cr{sub 3}Ge phase was determined by photoacoustic absorption spectroscopy measurements.

  19. Spin pumping and inverse Rashba-Edelstein effect in NiFe/Ag/Bi and NiFe/Ag/Sb

    SciTech Connect

    Zhang, Wei Jungfleisch, Matthias B.; Jiang, Wanjun; Pearson, John E.; Hoffmann, Axel

    2015-05-07

    The Rashba effect is an interaction between the spin and the momentum of electrons induced by the spin-orbit coupling in surface or interface states. We measured the inverse Rashba-Edelstein effect via spin pumping in Ag/Bi and Ag/Sb interfaces. The spin current is injected from the ferromagnetic resonance of a NiFe layer towards the Rashba interfaces, where it is further converted into a charge current. Using spin pumping theory, we quantify the conversion parameter of spin to charge current to be 0.11 ± 0.02 nm for Ag/Bi and a factor of ten smaller for Ag/Sb. The relative strength of the effect is in agreement with spectroscopic measurements and first principles calculations. We also vary the interlayer materials to study the voltage output in relation to the change of the effective spin mixing conductance. The spin pumping experiment offers a straight-forward approach of using spin current as an efficient probe for detecting interface Rashba splitting.

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

    SciTech Connect

    Saravanan, P.; Hsu, Jen-Hwa Tsai, C. L.; Tsai, C. Y.; Lin, Y. H.; Kuo, C. Y.; Wu, J.-C.; Lee, C.-M.

    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 analysis 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.

  1. The effects of fuel type in synthesis of NiFe2O4 nanoparticles by microwave assisted combustion method

    NASA Astrophysics Data System (ADS)

    Karcıoğlu Karakaş, Zeynep; Boncukçuoğlu, Recep; Karakaş, İbrahim H.

    2016-04-01

    In this study, it was investigated the effects of the used fuels on structural, morphological and magnetic properties of nanoparticles in nanoparticle synthesis with microwave assisted combustion method with an important method in quick, simple and low cost at synthesis of the nanoparticles. In this aim, glycine, urea and citric acid were used as fuel, respectively. The synthesised nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmet-Teller surface area (BET), and vibrating sample magnetometry (VSM) techniques. We observed that fuel type is quite effective on magnetic properties and surface properties of the nanoparticles. X-ray difractograms of the obtained nanoparticles were compared with standard powder diffraction cards of NiFe2O4 (JCPDS Card Number 54-0964). The results demonstrated that difractograms are fully compatible with standard reflection peaks. According to the results of the XRD analysis, the highest crystallinity was observed at nanoparticles synthesized with glycine. The results demonstrated that the nanoparticles prepared with urea has the highest surface area. The micrographs of SEM showed that all of the nanoparticles have nano-crystalline behaviour and particles indication cubic shape. VSM analysis demonstrated that the type of fuel used for synthesis is highly effective a parameter on magnetic properties of nanoparticles.

  2. [NiFe]Hydrogenase from Citrobacter sp. S-77 surpasses platinum as an electrode for H2 oxidation reaction.

    PubMed

    Matsumoto, Takahiro; Eguchi, Shigenobu; Nakai, Hidetaka; Hibino, Takashi; Yoon, Ki-Seok; Ogo, Seiji

    2014-08-18

    Reported herein is an electrode for dihydrogen (H2) oxidation, and it is based on [NiFe]Hydrogenase from Citrobacter sp. S-77 ([NiFe]S77). It has a 637 times higher mass activity than Pt (calculated based on 1 mg of [NiFe]S77 or Pt) at 50 mV in a hydrogen half-cell. The [NiFe]S77 electrode is also stable in air and, unlike Pt, can be recovered 100 % after poisoning by carbon monoxide. Following characterization of the [NiFe]S77 electrode, a fuel cell comprising a [NiFe]S77 anode and Pt cathode was constructed and shown to have a a higher power density than that achievable by Pt. PMID:24895095

  3. [NiFe]Hydrogenase from Citrobacter sp. S-77 surpasses platinum as an electrode for H2 oxidation reaction.

    PubMed

    Matsumoto, Takahiro; Eguchi, Shigenobu; Nakai, Hidetaka; Hibino, Takashi; Yoon, Ki-Seok; Ogo, Seiji

    2014-08-18

    Reported herein is an electrode for dihydrogen (H2) oxidation, and it is based on [NiFe]Hydrogenase from Citrobacter sp. S-77 ([NiFe]S77). It has a 637 times higher mass activity than Pt (calculated based on 1 mg of [NiFe]S77 or Pt) at 50 mV in a hydrogen half-cell. The [NiFe]S77 electrode is also stable in air and, unlike Pt, can be recovered 100 % after poisoning by carbon monoxide. Following characterization of the [NiFe]S77 electrode, a fuel cell comprising a [NiFe]S77 anode and Pt cathode was constructed and shown to have a a higher power density than that achievable by Pt.

  4. Purification and Characterization of [NiFe]-Hydrogenase of Shewanella oneidensis MR-1

    SciTech Connect

    Shi, Liang; Belchik, Sara M.; Plymale, Andrew E.; Heald, Steve M.; Dohnalkova, Alice; Sybirna, Kateryna; Bottin, Herve; Squier, Thomas C.; Zachara, John M.; Fredrickson, Jim K.

    2011-08-02

    The γ-proteobacterium Shewanella oneidensis MR-1 possesses a periplasmic [NiFe]-hydrogenase (MR-1 [NiFe]-H2ase) that was implicated in both H2 production and oxidation as well as technetium [Tc(VII)] reduction. To characterize the roles of MR-1 [NiFe]-H2ase in these proposed reactions, the genes encoding both subunits of MR-1 [NiFe]-H2ase were cloned into a protein expression vector. The resulting plasmid was transformed into a MR-1 mutant deficient in H2 formation. Expression of MR-1 [NiFe]-H2ase in trans restored the mutant’s ability to produce H2 at 37% of that for wild type. Following expression, MR-1 [NiFe]-H2ase was purified to near homogeneity. The purified MR-1 [NiFe]-H2ase could couple H2 oxidation to reduction of Tc(VII) and methyl viologen directly. Change of the buffers used affected MR-1 [NiFe]-H2ase-mediated Tc(VII) but not methyl viologen reductions. Under the conditions tested, Tc(VII) reduction was complete in Tris buffer but not in HEPES buffer. The reduced Tc(IV) was soluble in Tris buffer but insoluble in HEPES buffer. Transmission electron microscopy analysis revealed that Tc(IV) precipitates formed in HEPES buffer were packed with crystallites. Although X-ray absorption near-edge spectroscopy measurements confirmed that the reduction products found in both buffers were Tc(IV), extended X-ray adsorption fine-structure measurements revealed that these products were very different. While the product in Tris buffer could not be determined, the Tc(IV) product in HEPES buffer was very similar to Tc(IV)O2•nH2O. These results shows for the first time that MR-1 [NiFe]-H2ase is a bidirectional enzyme that catalyzes both H2 formation and oxidation as well as Tc(VII) reduction directly by coupling H2 oxidation.

  5. Physical and electrical characteristics of NiFe thin films using ultrasonic assisted pulse electrodeposition

    NASA Astrophysics Data System (ADS)

    Asa Deepthi, K.; Balachandran, R.; Ong, B. H.; Tan, K. B.; Wong, H. Y.; Yow, H. K.; Srimala, S.

    2016-01-01

    Nickel iron (NiFe) thin films were prepared on the copper substrate by ultrasonic assisted pulse electrodeposition under galvanostatic mode. Careful control of the thin films deposition is essential as the electrical properties of the films could be greatly affected, particularly if low quality films are produced. The preparation of NiFe/Cu thin films was aimed to reduce the grain size of NiFe particles, surface roughness and electrical resistivity of the copper substrates. Various parameters were systematically studied including current magnitude, deposition time and ultrasonic bath temperature. The optimized conditions to obtain NiFe permalloy, which subsequently applied to all investigated samples, were found at a current magnitude of 70 mA deposited for a duration of 2 min under ultrasonic bath temperature of 27 °C. The composition of NiFe permalloy was as close as Ni 80.71% and Fe 19.29% and the surface roughness was reduced from 12.76 nm to 2.25 nm. The films electrical resistivity was decreased nearly sevenfold from an initial value of 67.32 μΩ cm to 9.46 μΩ cm.

  6. Catalytic dechlorination of Aroclor 1242 by Ni/Fe bimetallic nanoparticles.

    PubMed

    Zhang, Zhen; Hu, Sai; Baig, Shams Ali; Tang, Jie; Xu, Xinhua

    2012-11-01

    Ni/Fe bimetallic nanoparticles were synthesized for treatment of Aroclor 1242, in order to evaluate their applicability for in situ remediation of groundwater and soil contaminated by polychlorinated biphenyls (PCBs). Our experimental results indicate that the total PCB concentration changed during the reduction of 3,5-dichlorobiphenyl (PCB 14), and biphenyl was produced as the final product. Initially, the concentration of 3-chlorobiphenyl (PCB 2) was increased in the prophase reaction and then slowly decreased, suggesting that Aroclor 1242 was first adsorbed by Ni/Fe nanoparticles, and then, the higher chlorinated congeners were converted gradually to the lower chlorinated congeners, and finally to biphenyl. The dechlorination efficiency of Aroclor 1242 reached approximately 80% at 25°C in just 5h, then 95.6% and 95.8% in 10h and 24h, respectively. The study revealed that high Ni/Fe nanoparticle dosage and high Ni content in Ni/Fe nanoparticles favor the catalytic dechlorination reaction. Moreover, a comparison of different types of catalysts on the dechlorination of Aroclor 1242 indicated that Ni/Mg and Mg powders showed a greater reactivity than Ni/Fe and Fe nanoparticles, respectively.

  7. Mechanism of inhibition of NiFe hydrogenase by nitric oxide.

    PubMed

    Ceccaldi, Pierre; Etienne, Emilien; Dementin, Sébastien; Guigliarelli, Bruno; Léger, Christophe; Burlat, Bénédicte

    2016-04-01

    Hydrogenases reversibly catalyze the oxidation of molecular hydrogen and are inhibited by several small molecules including O2, CO and NO. In the present work, we investigate the mechanism of inhibition by NO of the oxygen-sensitive NiFe hydrogenase from Desulfovibrio fructosovorans by coupling site-directed mutagenesis, protein film voltammetry (PFV) and EPR spectroscopy. We show that micromolar NO strongly inhibits NiFe hydrogenase and that the mechanism of inhibition is complex, with NO targeting several metallic sites in the protein. NO reacts readily at the NiFe active site according to a two-step mechanism. The first and faster step is the reversible binding of NO to the active site followed by a slower and irreversible transformation at the active site. NO also induces irreversible damage of the iron-sulfur centers chain. We give direct evidence of preferential nitrosylation of the medial [3Fe-4S] to form dinitrosyl-iron complexes. PMID:26827939

  8. Electric-field tunable spin diode FMR in patterned PMN-PT/NiFe structures

    NASA Astrophysics Data System (ADS)

    Zietek, Slawomir; Ogrodnik, Piotr; Skowroński, Witold; Stobiecki, Feliks; van Dijken, Sebastiaan; Barnaś, Józef; Stobiecki, Tomasz

    2016-08-01

    Dynamic properties of NiFe thin films on PMN-PT piezoelectric substrate are investigated using the spin-diode method. Ferromagnetic resonance (FMR) spectra of microstrips with varying width are measured as a function of magnetic field and frequency. The FMR frequency is shown to depend on the electric field applied across the substrate, which induces strain in the NiFe layer. Electric field tunability of up to 100 MHz per 1 kV/cm is achieved. An analytical model based on total energy minimization and the Landau-Lifshitz-Gilbert equation, taking into account the magnetostriction effect, is used to explain the measured dynamics. Based on this model, conditions for optimal electric-field tunable spin diode FMR in patterned NiFe/PMN-PT structures are derived.

  9. Electrochemical insights into the mechanism of NiFe membrane-bound hydrogenases

    PubMed Central

    Flanagan, Lindsey A.; Parkin, Alison

    2016-01-01

    Hydrogenases are enzymes of great biotechnological relevance because they catalyse the interconversion of H2, water (protons) and electricity using non-precious metal catalytic active sites. Electrochemical studies into the reactivity of NiFe membrane-bound hydrogenases (MBH) have provided a particularly detailed insight into the reactivity and mechanism of this group of enzymes. Significantly, the control centre for enabling O2 tolerance has been revealed as the electron-transfer relay of FeS clusters, rather than the NiFe bimetallic active site. The present review paper will discuss how electrochemistry results have complemented those obtained from structural and spectroscopic studies, to present a complete picture of our current understanding of NiFe MBH. PMID:26862221

  10. Magnetic resonance of the NiFe2O4 nanoparticles in the gigahertz range

    PubMed Central

    2013-01-01

    We report an adjustable magnetic resonance frequency from 1.45 to 2.54 GHz for NiFe2O4 nanoparticles which were prepared by a sol–gel process. X-ray diffraction and scanning electron microscopy results indicate that the samples are polycrystalline nanoparticles, and the size of the particles increases obviously with the thermal treatment temperature. The consequence of the surface composition suggests that the oxygen defects are present in the nanoparticle surface, and this surface magnetic state can show a strong surface anisotropy. With decreasing size of the particle, the surface magnetic effect is predominant, resulting in an increase of resonance frequency for NiFe2O4 nanoparticles. This finding provides a new route for NiFe2O4 materials that can be used in the gigahertz range. PMID:24083340

  11. Tensile Properties and Deformation Characteristics of a Ni-Fe-Base Superalloy for Steam Boiler Applications

    NASA Astrophysics Data System (ADS)

    Zhong, Zhihong; Gu, Yuefeng; Yuan, Yong; Shi, Zhan

    2014-01-01

    Ni-Fe-base superalloys due to their good manufacturability and low cost are the proper candidates for boiler materials in advanced power plants. The major concerns with Ni-Fe-base superalloys are the insufficient mechanical properties at elevated temperatures. In this paper, tensile properties, deformation, and fracture characteristics of a Ni-Fe-base superalloy primarily strengthened by γ' precipitates have been investigated from room temperature to 1073 K (800 °C). The results showed a gradual decrease in the strength up to about 973 K (700 °C) followed by a rapid drop above this temperature and a ductility minimum at around 973 K (700 °C). The fracture surfaces were studied using scanning electron microscopy and the deformation mechanisms were determined by the observation of deformed microstructures using transmission electron microscopy. An attempt has been made to correlate the tensile properties and fracture characteristics at different temperatures with the observed deformation mechanisms.

  12. Atomic simulation of mechanical behavior of Mg in a super-lattice of nanocrystalline Mg and amorphous Mg-Al alloy

    SciTech Connect

    Song, H. Y.; An, M. R.; Li, Y. L. Deng, Q.

    2014-12-07

    The mechanical properties of a super-lattice architecture composed of nanocrystalline Mg and Mg-Al amorphous alloy are investigated using molecular dynamics simulation. The results indicate that deformation mechanism of nanocrystalline Mg is obviously affected by the amorphous boundary spacing and temperature. The strength of the material increases with the decrease of amorphous boundary spacing, presenting a Hall-Petch effect at both 10 K and 300 K. A stress platform and following stiffness softening, as well as a linear strengthening in the plastic stage, are observed when the amorphous boundary spacing below 8.792 nm at 10 K. The implying reason may be that the amorphous boundary acts as the dislocations emission and absorption source. However, the second stress peak is not observed for the models at 300 K. Instead, the flow stress in plastic stage is a nearly constant value. The simulation demonstrates the emergence of the new grain, accompanied by the deformation twins and stacking faults associated with the plastic behaviors at 300 K. The general conclusions derived from this work may provide a guideline for the design of high-performance hexagonal close-packed metals.

  13. Optimization of planar Hall effect sensor for magnetic bead detection using spin-valve NiFe/Cu/NiFe/IrMn structures

    NASA Astrophysics Data System (ADS)

    Tu, Bui Dinh; Viet Cuong, Le; Thi Huong Giang, Do; Mau Danh, Tran; Duc, Nguyen Huu

    2009-09-01

    Present paper deals with the planar Hall effect (PHE) of Ta(5 nm)/NiFe(tf)/Cu(1.2 nm)/NiFe(tp)/IrMn(15 nm)/Ta(5 nm) spin-valve structures. Experimental investigations are performed for 50 × 50 μm2 junctions with various thicknesses of free and pinned layer tf = 4, 8, 10, 15, 20 nm and tp = 2, 3, 6, 8, 9, 12 nm. The results show that the thicker free layers, the higher PHE signal is obtained. In addition, the thicker pinned layers, the lower PHE signal. The highest PHE sensitivity S of 15.6 mΩ/Oe is obtained in the spin-valve configuration with tf = 20 nm and tp = 2 nm. This optimum structure is rather promising for micro magnetic bead detections.

  14. Purification and Characterization of the [NiFe]-Hydrogenase of Shewanella oneidensis MR-1 ▿

    PubMed Central

    Shi, Liang; Belchik, Sara M.; Plymale, Andrew E.; Heald, Steve; Dohnalkova, Alice C.; Sybirna, Kateryna; Bottin, Hervé; Squier, Thomas C.; Zachara, John M.; Fredrickson, James K.

    2011-01-01

    Shewanella oneidensis MR-1 possesses a periplasmic [NiFe]-hydrogenase (MR-1 [NiFe]-H2ase) that has been implicated in H2 production and oxidation as well as technetium [Tc(VII)] reduction. To characterize the roles of MR-1 [NiFe]-H2ase in these proposed reactions, the genes encoding both subunits of MR-1 [NiFe]-H2ase were cloned and then expressed in an MR-1 mutant without hyaB and hydA genes. Expression of recombinant MR-1 [NiFe]-H2ase in trans restored the mutant's ability to produce H2 at 37% of that for the wild type. Following purification, MR-1 [NiFe]-H2ase coupled H2 oxidation to reduction of Tc(VII)O4− and methyl viologen. Change of the buffers used affected MR-1 [NiFe]-H2ase-mediated reduction of Tc(VII)O4− but not methyl viologen. Under the conditions tested, all Tc(VII)O4− used was reduced in Tris buffer, while in HEPES buffer, only 20% of Tc(VII)O4− was reduced. The reduced products were soluble in Tris buffer but insoluble in HEPES buffer. Transmission electron microscopy analysis revealed that Tc precipitates reduced in HEPES buffer were aggregates of crystallites with diameters of ∼5 nm. Measurements with X-ray absorption near-edge spectroscopy revealed that the reduction products were a mixture of Tc(IV) and Tc(V) in Tris buffer but only Tc(IV) in HEPES buffer. Measurements with extended X-ray adsorption fine structure showed that while the Tc bonding environment in Tris buffer could not be determined, the Tc(IV) product in HEPES buffer was very similar to Tc(IV)O2·nH2O, which was also the product of Tc(VII)O4− reduction by MR-1 cells. These results shows for the first time that MR-1 [NiFe]-H2ase catalyzes Tc(VII)O4− reduction directly by coupling to H2 oxidation. PMID:21724888

  15. Study of magnetic behavior in ball-milled nanocrystalline Fe-50 at.%Al alloy as a function of milling time

    NASA Astrophysics Data System (ADS)

    Rajan, S.; Shukla, R.; Kumar, A.; Vyas, A.; Brajpuriya, R.

    2015-04-01

    Ball milling technique has been extensively used to prepare different metastable states with nanocrystalline microstructures from intermetallic compounds. The present study was made on the identification of the changes in magnetic and electronic properties as a result of high-energy ball milling of Fe-50 at.%Al alloy samples. The phase formation and physical properties of the alloys were determined as a function of milling time by means of Mössbauer and X-ray photoelectron spectroscopy (XPS). The Mössbauer results show the formation of nanostructured body-centered cubic (BCC) FeAl alloy only after 5 h of mechanical milling and the same is also confirmed by Scanning electron microscope (SEM) and Transmission electron microscopy (TEM) studies. Mössbauer studies further confirm that there is magnetic behavior retention in the FeAl alloy samples even after 5 h of milling but magnetization decreases as the milling time increases. The reason for the same is due to the shocks and fracturing of the Al atoms embedded in the sites of Fe and as a result of which Fe-Fe nearest neighbors decreases. Secondly, with the increase in milling time, the particle size and the number density of equiatomic BCC Fe50Al50 grains decrease while the volume of grain boundary containing a solid solution of BCC FeAl and concentration of Al in a solid solution of BCC FeAl at the grain boundary increases as a result of which magnetization decreases. The shift in the binding energy of Fe2p and Al2p core level towards higher binding energy also supports the alloy formation after milling.

  16. Preparation, characterization, and antibacterial activity of NiFe2O4/PAMA/Ag-TiO2 nanocomposite

    NASA Astrophysics Data System (ADS)

    Allafchian, Alireza; Jalali, Seyed Amir Hossein; Bahramian, Hamid; Ahmadvand, Hossein

    2016-04-01

    We have described a facile fabrication of silver deposited on the TiO2, Poly Acrylonitrile Co Maleic Anhydride (PAMA) polymer and nickel ferrite composite (NiFe2O4/PAMA/Ag-TiO2) through a three-step procedure. A pre-synthesized NiFe2O4 was first coated with PAMA polymer and then Ag-TiO2 was deposited on the surface of PAMA polymer shell. After the characterization of this three-component composite by various techniques, such as FTIR, XRD, FESEM, BET, TEM and VSM, it was impregnated in standard antibiotic discs. The antibacterial activity of NiFe2O4/PAMA/Ag-TiO2 nanocomposite was investigated against some gram positive and gram negative bacteria by employing disc diffusion assay and then compared with that of naked NiFe2O4, NiFe2O4/Ag, AgNPs and NiFe2O4/PAMA. The results demonstrated that the AgNPs, when embedded in TiO2 and combined with NiFe2O4/PAMA, became an excellent antibacterial agent. The NiFe2O4/PAMA/Ag-TiO2 nanocomposite could be readily separated from water solution after the disinfection process by applying an external magnetic field.

  17. Exchange anisotropy and micromagnetic properties of PtMn/NiFe bilayers

    NASA Astrophysics Data System (ADS)

    Pokhil, Taras; Linville, Eric; Mao, Sining

    2001-06-01

    Magnetic microstructure, exchange induced uniaxial and unidirectional anisotropy and structural transformation have been studied in PtMn/NiFe bilayer films and small elements as a function of annealing time. The relationship between the fcc-fct ordering phase transformation in PtMn and the development of exchange induced magnetic properties in PtMn/NiFe bilayers is complicated by the fact that the transformation occurs throughout the entire volume of the PtMn film, while the exchange between the layers is predominantly an interface effect. Consequently, the development of the exchange anisotropy should depend primarily on the character of the structural transformation at the interface between PtMn and NiFe. The purpose of this article is to correlate the volume phase transformation in PtMn to the development of exchange anisotropy and micromagnetic behavior in PtMn/NiFe bilayers. The interface structure can be inferred from the anisotropy and micromagnetic measurements, leading to a model that explains the relationship between the volume and interface transformation structures in PtMn, and magnetic properties of the bilayers. The structure and magnetic properties were characterized by x-ray diffraction, vibrating sample magnetometry, and magnetic force microscopy.

  18. The enhanced exchange coupled interaction in nanocrystalline Nd2Fe14B/Fe3B+ αFe alloys with improved microstructure

    NASA Astrophysics Data System (ADS)

    Gao, Youhui; Zhu, Jinghan; Weng, Yuqing; Byung Park, Eon; Jin Yang, Choong

    1999-01-01

    The effects of additives and heat-treatment conditions on the microstructure in nanocrystalline alloy Nd 2Fe 14B/Fe 3B+αFe were studied using H c(T)/M s(T) versus 2k 1(T)/μ 0M 2s(T) plots, TEM, and Mössbauer spectroscopy in this paper. It was found that the additives Hf and Ga improve the condition of the grain shapes, but simultaneously deteriorate the grain surfaces. Magnetic field heat-treatment not only induces grain refinement but also causes a uniform distribution of the soft and hard phases in this nanocomposite alloy. The influences of Hf, Ga and magnetic field heat-treatment are weakened upon increasing the annealing temperature. Furthermore, the magnetic interaction was examined using δM plot in this paper. It was found that the exchange coupled interaction is greatly enhanced in the sample annealed with magnetic heat-treatment, which has the highest energy product of (BH) max=15.8 MG Oe.

  19. Grain boundary segregation and interdiffusion effects in nickel-copper alloys: an effective means to improve the thermal stability of nanocrystalline nickel.

    PubMed

    Pellicer, Eva; Varea, Aïda; Sivaraman, Kartik M; Pané, Salvador; Suriñach, Santiago; Baró, Maria Dolors; Nogués, Josep; Nelson, Bradley J; Sort, Jordi

    2011-07-01

    Nanocrystalline (nc) Ni films show pronounced grain growth and suffer from concomitant deterioration of their mechanical and magnetic properties after annealing at relatively low temperatures (T(ANN) ≥ 475 K). This constitutes a drawback for their applicability as coatings or in components of miniaturized devices. This work reveals that the thermal stability of nc Ni is significantly improved by controllably alloying Ni with Cu, by means of electrodeposition, to form a Ni(1-x)Cu(x) solid solution. To tune the composition of such nc alloys, Ni(1-x)Cu(x) films are deposited galvanostatically using an electrolytic bath containing Ni and Cu sulfate salts as electroactive species, saccharine as grain-refining agent, and applying current densities ranging from -10 to -40 mA cm(-2). The enhanced thermal stability is ascribed to segregation of a Cu-rich phase at the Ni(1-x)Cu(x) grain boundaries, which acts as a shielding layer against grain growth. As a result, high values of hardness (in excess of 6 GPa) remain in nc Ni(1-x)Cu(x) for x ≥ 0.3, even after annealing at T(ANN) ≥ 575 K. From a magnetic point of view, Ni(1-x)Cu(x) films possess lower coercivity values than pure nc Ni films, both in the as-prepared and annealed states, thus offering potential advantages for certain soft magnetic applications. PMID:21667966

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

    PubMed

    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.

  1. Fabrication of Magnetic NiFe2O4 Nanorods and Their Removal Performances of Congo Red.

    PubMed

    Li, Yunlong; Lu, Lu; Li, Xiuping; Chen, Dan; Ma, Liyu; Liu, Ruijiang

    2016-06-01

    Magnetic NiFe2O4 nanorods were prepared successfully via a facile solution combustion process, the morphology, chemical composition, microstructure and magnetic properties of as-prepared NiFe2O4 nanorods were investigated by XRD, VSM, SEM, TEM, EDX, SAED and BET techniques. The magnetic NiFe2O4 nanorods were characterized with average length of about 130 nm, the diameter of around 25 nm, the specific magnetization of 105.2 Am2/kg, and the specific surface area of 88.8 m2/g. The nanorods were employed to remove congo red (CR) from aqueous solutions, the adsorption kinetic and adsorption isotherm of CR onto NiFe2O4 nanorods at room temperature were investigated. The regression equation was found in good agreement with the pseudo-second-order kinetic model in a range of initial CR concentrations of 80-400 mg/L. Compared with Freundlich and Temkin models, Langmuir model fitted the adsorption isotherm of CR onto NiFe2O4 nanorods better, which suggested that the adsorption of CR onto NiFe2O4 nanorods was a monolayer absorbing mechanism. Meanwhile, the adsorption capacity of CR onto NiFe2O4 nanorods is large when pH is less than 9. PMID:27427682

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

    SciTech Connect

    Gubbiotti, G. Tacchi, S.; Del Bianco, L.; Bonfiglioli, E.; Giovannini, L.; Spizzo, F.; Zivieri, R.; Tamisari, M.

    2015-05-07

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

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

    NASA Astrophysics Data System (ADS)

    Gubbiotti, G.; Tacchi, S.; Del Bianco, L.; Bonfiglioli, E.; Giovannini, L.; Tamisari, M.; Spizzo, F.; Zivieri, R.

    2015-05-01

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

  4. Thermodynamic analysis of binary Fe85B15 to quinary Fe85Si2B8P4Cu1 alloys for primary crystallizations of α-Fe in nanocrystalline soft magnetic alloys

    NASA Astrophysics Data System (ADS)

    Takeuchi, A.; Zhang, Y.; Takenaka, K.; Makino, A.

    2015-05-01

    Fe-based Fe85B15, Fe84B15Cu1, Fe82Si2B15Cu1, Fe85Si2B12Cu1, and Fe85Si2B8P4Cu1 (NANOMET®) alloys were experimental and computational analyzed to clarify the features of NANOMET that exhibits high saturation magnetic flux density (Bs) nearly 1.9 T and low core loss than conventional nanocrystalline soft magnetic alloys. The X-ray diffraction analysis for ribbon specimens produced experimentally by melt spinning from melts revealed that the samples were almost formed into an amorphous single phase. Then, the as-quenched samples were analyzed with differential scanning calorimeter (DSC) experimentally for exothermic enthalpies of the primary and secondary crystallizations (ΔHx1 and ΔHx2) and their crystallization temperatures (Tx1 and Tx2), respectively. The ratio ΔHx1/ΔHx2 measured by DSC experimentally tended to be extremely high for the Fe85Si2B8P4Cu1 alloy, and this tendency was reproduced by the analysis with commercial software, Thermo-Calc, with database for Fe-based alloys, TCFE7 for Gibbs free energy (G) assessments. The calculations exhibit that a volume fraction (Vf) of α-Fe tends to increase from 0.56 for the Fe85B15 to 0.75 for the Fe85Si2B8P4Cu1 alloy. The computational analysis of the alloys for G of α-Fe and amorphous phases (Gα-Fe and Gamor) shows that a relationship Gα-Fe ˜ Gamor holds for the Fe85Si2B12Cu1, whereas Gα-Fe < Gamor for the Fe85Si2B8P4Cu1 alloy at Tx1 and that an extremely high Vf = 0.75 was achieved for the Fe85Si2B8P4Cu1 alloy by including 2.8 at. % Si and 4.5 at. % P into α-Fe. These computational results indicate that the Fe85Si2B8P4Cu1 alloy barely forms amorphous phase, which, in turn, leads to high Vf and resultant high Bs.

  5. Morphology and composition of chalcopyrite, chromite, Cu, Ni-Fe, pentlandite, and troilite in vugs of 76015 and 76215

    NASA Technical Reports Server (NTRS)

    Carter, J. L.; Clanton, U. S.; Laughon, R. B.; Mckay, D. S.; Usselman, T. M.; Fuhrman, R.

    1975-01-01

    Vugs from 76015 and 76215 are lined with euhedral crystals of plagioclase, pyroxene, ilmenite, Ni-Fe, and troilite. Smaller crystals of chromite, pentlandite, and chalcopyrite occur on the surface of the troilite in 76015. Wire Cu and dendritic-metallic Cu occurs with metallic Ni-Fe and troilite in some vugs of 76215. Troilite in both samples may have crystallized from an immiscible sulfide liquid. With falling temperature, chalcopyrite, and pentlandite may have exsolved from the troilite in 76015. By contrast, metallic Cu may have formed in 76215 by thermal breakdown of a bornite, troilite, and Ni-Fe assemblage which originally crystallized from a low-Ni immiscible sulfide liquid.

  6. Electrodeposited anisotropic NiFe 45/55 thin films for high-frequency micro-inductor applications

    NASA Astrophysics Data System (ADS)

    O'Donnell, Terence; Wang, Ningning; Kulkarni, Santosh; Meere, Ronan; Rhen, Fernando M. F.; Roy, Saibal; O'Mathuna, S. C.

    2010-05-01

    Micro-inductors, with an electrodeposited nickel-iron core have been fabricated on silicon substrates, and have been characterized in the frequency range up to 100 MHz. The core consists of a nickel iron, 45:55 alloy which is deposited using pulse-reverse electroplating in the presence of a magnetic field to control anisotropy. The operation of the inductors with low loss at high-frequency critically depends on core thickness, which is used to control eddy-current loss as the frequency is increased. However, it is shown that the permeability of NiFe 45/55 has a dependency on thickness, and decreases with increasing thickness. For example, the permeability is measured to be approximately 1000 for a 1-μm-thick film, decreasing to approximately 400 for a 5-μm-thick film. In order to correctly design micro-inductors for operation up to 100 MHz, it is important that this characteristic of the material is taken into account.

  7. Microstructure, magnetic, and magnetoimpedance properties of electrodeposited NiFe/Cu and CoNiFe/Cu wire: A study on influence of saccharin additive in plating bath

    NASA Astrophysics Data System (ADS)

    Mishra, Amaresh Chandra; Sahoo, Trilochan; Srinivas, V.; Thakur, Awalendra K.

    2011-04-01

    Magnetic thin films of NiFe and CoNiFe were electrodeposited from three different deposition baths on copper wires of 100 μm diameter. The magnetic and magneto-impedance (MI) properties of the samples were investigated as a function of saccharin additive concentration in the plating bath. For all intermediate frequencies, the MI ratio increased with saccharin concentration in the plating bath up to a critical concentration and then saturates. The change in MI with saccharin concentration in electrodeposition bath was attributed to the grain size reducing action of saccharin which in turn reduces the coercivity of the film, making it soft magnetic. The origin of MI lies in the combined effect of domain wall motion and spin rotation which contributes to permeability. Inductance spectroscopy was used to evaluate the magnetic characteristic of the samples by modeling magnetic film-coated wires in terms of equivalent electrical circuit; namely parallel inductance and resistance circuit in series with series A circuit. The domain wall motion was found to be greatly affected by saccharin addition to the bath, which was revealed through the study of variations in these circuit parameters. The domain wall motion thereby affects the magnetic softness of samples, which is reflected by MI enhancement.

  8. Room temperature spin valve effect in NiFe/WS2/Co junctions

    PubMed Central

    Iqbal, Muhammad Zahir; Iqbal, Muhammad Waqas; Siddique, Salma; Khan, Muhammad Farooq; Ramay, Shahid Mahmood

    2016-01-01

    The two-dimensional (2D) layered electronic materials of transition metal dichalcogenides (TMDCs) have been recently proposed as an emerging canddiate for spintronic applications. Here, we report the exfoliated single layer WS2-intelayer based spin valve effect in NiFe/WS2/Co junction from room temperature to 4.2 K. The ratio of relative magnetoresistance in spin valve effect increases from 0.18% at room temperature to 0.47% at 4.2 K. We observed that the junction resistance decreases monotonically as temperature is lowered. These results revealed that semiconducting WS2 thin film works as a metallic conducting interlayer between NiFe and Co electrodes. PMID:26868638

  9. Glycerol Steam Reforming Over Ni-Fe-Ce/Al2O3 Catalyst: Effect of Cerium.

    PubMed

    Go, Gwang-Sub; Go, Yoo-Jin; Lee, Hong-Joo; Moon, Dong-Ju; Park, Nam-Cook; Kim, Young-Chul

    2016-02-01

    In this work, hydrogen production from glycerol by steam reforming was studied using Ni-metal oxide catalysts. Ni-based catalyst becomes deactivated during steam reforming reactions because of coke deposits and sintering. Therefore, the aim of this study was to reduce carbon deposits and sintering on the catalyst surface by adding a promoter. Ni-metal oxide catalysts supported on Al2O3 were prepared via impregnation method, and the calcined catalyst was reduced under H2 flow for 2 h prior to the reaction. The characteristics of the catalysts were examined by XRD, TPR, TGA, and SEM. The Ni-Fe-Ce/Al2O3 catalyst, which contained less than 2 wt% Ce, showed the highest hydrogen selectivity and glycerol conversion. Further analysis of the catalysts revealed that the Ni-Fe-Ce/Al2O3 catalyst required a lower reduction temperature and produced minimum carbon deposit. PMID:27433687

  10. Glycerol Steam Reforming Over Ni-Fe-Ce/Al2O3 Catalyst: Effect of Cerium.

    PubMed

    Go, Gwang-Sub; Go, Yoo-Jin; Lee, Hong-Joo; Moon, Dong-Ju; Park, Nam-Cook; Kim, Young-Chul

    2016-02-01

    In this work, hydrogen production from glycerol by steam reforming was studied using Ni-metal oxide catalysts. Ni-based catalyst becomes deactivated during steam reforming reactions because of coke deposits and sintering. Therefore, the aim of this study was to reduce carbon deposits and sintering on the catalyst surface by adding a promoter. Ni-metal oxide catalysts supported on Al2O3 were prepared via impregnation method, and the calcined catalyst was reduced under H2 flow for 2 h prior to the reaction. The characteristics of the catalysts were examined by XRD, TPR, TGA, and SEM. The Ni-Fe-Ce/Al2O3 catalyst, which contained less than 2 wt% Ce, showed the highest hydrogen selectivity and glycerol conversion. Further analysis of the catalysts revealed that the Ni-Fe-Ce/Al2O3 catalyst required a lower reduction temperature and produced minimum carbon deposit.

  11. Effects of two-temperature model on cascade evolution in Ni and NiFe

    DOE PAGESBeta

    Samolyuk, German D.; Xue, Haizhou; Bei, Hongbin; Weber, William J.

    2016-07-05

    We perform molecular dynamics simulations of Ni ion cascades in Ni and equiatomic NiFe under the following conditions: (a) classical molecular dynamics (MD) simulations without consideration of electronic energy loss, (b) classical MD simulations with the electronic stopping included, and (c) using the coupled two-temperature MD (2T-MD) model that incorporates both the electronic stopping and the electron-phonon interactions. Our results indicate that the electronic e ects are more profound in the higher energy cascades and that the 2T-MD model results in a smaller amount of surviving damage and smaller defect clusters, while less damage is produced in NiFe than inmore » Ni.« less

  12. Effects of Sodium Citrate Concentration on Electroless Ni-Fe Bath Stability and Deposition

    NASA Astrophysics Data System (ADS)

    Jung, Myung-Won; Kang, Sung K.; Lee, Jae-Ho

    2014-01-01

    In this research, electroless Ni-Fe bath stability and deposition characteristics were investigated for various sodium citrate concentrations. Complexing agents such as sodium citrate are one of the main components of such electroless plating baths. Since they could play various roles such as maintaining pH stability, preventing precipitation of metal salts, and reducing the concentrations of free metal ions, the concentration of complexing agents in the plating bath is an important parameter for electroless deposition processes. In this research, unstable baths were obtained for insufficient sodium citrate concentrations, and these phenomena were analyzed with ChemEQL. Moreover, the deposition characteristics of electroless Ni-Fe for under bump metallurgy diffusion barriers were also investigated using energy-dispersive spectroscopy and field-emission scanning electron microscopy.

  13. Room temperature spin valve effect in NiFe/WS2/Co junctions

    NASA Astrophysics Data System (ADS)

    Iqbal, Muhammad Zahir; Iqbal, Muhammad Waqas; Siddique, Salma; Khan, Muhammad Farooq; Ramay, Shahid Mahmood

    2016-02-01

    The two-dimensional (2D) layered electronic materials of transition metal dichalcogenides (TMDCs) have been recently proposed as an emerging canddiate for spintronic applications. Here, we report the exfoliated single layer WS2-intelayer based spin valve effect in NiFe/WS2/Co junction from room temperature to 4.2 K. The ratio of relative magnetoresistance in spin valve effect increases from 0.18% at room temperature to 0.47% at 4.2 K. We observed that the junction resistance decreases monotonically as temperature is lowered. These results revealed that semiconducting WS2 thin film works as a metallic conducting interlayer between NiFe and Co electrodes.

  14. Room temperature spin valve effect in NiFe/WS₂/Co junctions.

    PubMed

    Iqbal, Muhammad Zahir; Iqbal, Muhammad Waqas; Siddique, Salma; Khan, Muhammad Farooq; Ramay, Shahid Mahmood

    2016-01-01

    The two-dimensional (2D) layered electronic materials of transition metal dichalcogenides (TMDCs) have been recently proposed as an emerging canddiate for spintronic applications. Here, we report the exfoliated single layer WS2-intelayer based spin valve effect in NiFe/WS2/Co junction from room temperature to 4.2 K. The ratio of relative magnetoresistance in spin valve effect increases from 0.18% at room temperature to 0.47% at 4.2 K. We observed that the junction resistance decreases monotonically as temperature is lowered. These results revealed that semiconducting WS2 thin film works as a metallic conducting interlayer between NiFe and Co electrodes. PMID:26868638

  15. Magnetic and electric behavior of NiFe2O4-PVDF nanocomposites

    NASA Astrophysics Data System (ADS)

    Sen, S.; Panda, A. K.; Prasad, K.

    2012-12-01

    NiFe2O4-PVDF composites in different ratios (10 %, 30 % and 50 %) were prepared in two steps. Firstly, fine nanosized NiFe2O4 powder was synthesized using the precursor solution method. Then the composites were made by hot-press technique. The presence of both the phases (ceramic and polymer) was confirmed by XRD micrographs. The average particle size of the composites varied from 18-23 nm. SEM micrographs showed that the ferrite particles were embedded in the polymer matrix. The saturation magnetization and the remanence showed an increasing trend with the increase in ferrite content while the coercivity remained almost constant. Impedance plot showed the presence of a single semicircle, which indicates the presence of bulk effect. The composites exhibited non-Debye relaxation. The bulk conductivity followed the Arrhenius type of behavior. The conduction mechanism was explained by the Vervey-de-Boer mechanism.

  16. Analysis of the weak coupling of the IrMn/Co/Ru/NiFe structures by ferromagnetic resonance

    SciTech Connect

    Alayo, W.; Baggio-Saitovitch, E.; Sousa, M. A.; Pelegrini, F.

    2011-04-15

    The Ir{sub 20}Mn{sub 80}/Co/Ru/Ni{sub 81}Fe{sub 19} spin valve structures have been produced by sputtering deposition and analyzed by ferromagnetic resonance. Two well resolved modes are identified in the FMR spectra as the resonance of the Co and NiFe layers. The in-plane angular dependence of the resonance peaks for the NiFe layer present a small asymmetry, which is attributed to the interlayer exchange interaction between ferromagnetic layers across the nonmagnetic spacer. The data were analyzed considering the exchange bias at the IrMn/Co interface and the indirect coupling between Co and NiFe. The in-plane angular dependence of the resonance fields of both Co and NiFe layers present an upward (downward) shift for antiferromagnetic (ferromagnetic) coupling with respect to a system with no interlayer coupling.

  17. Morphologically robust NiFe2O4 nanofibers as high capacity Li-ion battery anode material.

    PubMed

    Cherian, Christie Thomas; Sundaramurthy, Jayaraman; Reddy, M V; Suresh Kumar, Palanisamy; Mani, Kalaivani; Pliszka, Damian; Sow, Chorng Haur; Ramakrishna, Seeram; Chowdari, B V R

    2013-10-23

    In this work, the electrochemical performance of NiFe2O4 nanofibers synthesized by an electrospinning approach have been discussed in detail. Lithium storage properties of nanofibers are evaluated and compared with NiFe2O4 nanoparticles by galvanostatic cycling and cyclic voltammetry studies, both in half-cell configurations. Nanofibers exhibit a higher charge-storage capacity of 1000 mAh g(-1) even after 100 cycles with high Coulmbic efficiency of 100% between 10 and 100 cycles. Ex situ microscopy studies confirmed that cycled nanofiber electrodes maintained the morphology and remained intact even after 100 charge-discharge cycles. The NiFe2O4 nanofiber electrode does not experience any structural stress and eventual pulverisation during lithium cycling and hence provides an efficient electron conducting pathway. The excellent electrochemical performance of NiFe2O4 nanofibers is due to the unique porous morphology of continuous nanofibers.

  18. [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. PMID:25461840

  19. Energy-converting [NiFe] hydrogenases from archaea and extremophiles: ancestors of complex I.

    PubMed

    Hedderich, Reiner

    2004-02-01

    [NiFe] hydrogenases are well-characterized enzymes that have a key function in the H2 metabolism of various microorganisms. In the recent years a subfamily of [NiFe] hydrogenases with unique properties has been identified. The members of this family form multisubunit membrane-bound enzyme complexes composed of at least four hydrophilic and two integral membrane proteins. These six conserved subunits, which built the core of these hydrogenases, have closely related counterparts in energy-conserving NADH:quinone oxidoreductases (complex I). However, the reaction catalyzed by these hydrogenases differs significantly from the reaction catalyzed by complex I. For some of these hydrogenases the physiological role is to catalyze the reduction of H+ with electrons derived from reduced ferredoxins or poly-ferredoxins. This exergonic reaction is coupled to energy conservation by means of electron-transport phosphorylation. Other members of this hydrogenase family mainly function to provide the cell with reduced ferredoxin with H2 as electron donor in a reaction driven by reverse electron transport. As complex I these hydrogenases function as ion pumps and have therefore been designated as energy-converting [NiFe] hydrogenases.

  20. Magnetic properties of Ni-Fe nanowire arrays: effect of template material and deposition conditions

    SciTech Connect

    Singleton, John; Aravamudhan, Shyan; Goddard, Paul A; Bhansali, Shekhar

    2008-01-01

    The objective of this work is to study the magnetic properties of arrays of Ni-Fe nanowires electrodeposited in different template materials such as porous silicon, polycarbonate and alumina. Magnetic properties were studied as a function of template material, applied magnetic field (parallel and perpendicular) during deposition, wire length, as well as magnetic field orientation during measurement. The results show that application of magnetic field during deposition strongly influences the c-axis preferred orientation growth of Ni-Fe nanowires. The samples with magnetic field perpendicular to template plane during deposition exhibits strong perpendicular anisotropy with greatly enhanced coercivity and squareness ratio, particularly in Ni-Fe nanowires deposited in polycarbonate templates. In case of polycarbonate template, as magnetic field during deposition increases, both coercivity and squareness ratio also increase. The wire length dependence was also measured for polycarbonate templates. As wire length increases, coercivity and squarness ratio decrease, but saturation field increases. Such magnetic behavior (dependence on template material, magnetic field, wire length) can be qualitatively explained by preferential growth phenomena, dipolar interactions among nanowires, and perpendicular shape anisotropy in individual nanowires.

  1. Structural differences between the ready and unready oxidized states of [NiFe] hydrogenases.

    PubMed

    Volbeda, Anne; Martin, Lydie; Cavazza, Christine; Matho, Michaël; Faber, Bart W; Roseboom, Winfried; Albracht, Simon P J; Garcin, Elsa; Rousset, Marc; Fontecilla-Camps, Juan C

    2005-05-01

    [NiFe] hydrogenases catalyze the reversible heterolytic cleavage of molecular hydrogen. Several oxidized, inactive states of these enzymes are known that are distinguishable by their very different activation properties. So far, the structural basis for this difference has not been understood because of lack of relevant crystallographic data. Here, we present the crystal structure of the ready Ni-B state of Desulfovibrio fructosovorans [NiFe] hydrogenase and show it to have a putative mu-hydroxo Ni-Fe bridging ligand at the active site. On the other hand, a new, improved refinement procedure of the X-ray diffraction data obtained for putative unready Ni-A/Ni-SU states resulted in a more elongated electron density for the bridging ligand, suggesting that it is a diatomic species. The slow activation of the Ni-A state, compared with the rapid activation of the Ni-B state, is therefore proposed to result from the different chemical nature of the ligands in the two oxidized species. Our results along with very recent electrochemical studies suggest that the diatomic ligand could be hydro-peroxide. PMID:15803334

  2. He, Ne and Ar in chondritic Ni-Fe as irradiation hardness sensors.

    NASA Technical Reports Server (NTRS)

    Nyquist, L.; Funk, H.; Schultz, L.; Signer, P.

    1973-01-01

    Noble gas analyses of the Ni-Fe of 9 L, 5 H, and 2 LL chondrites quantitatively support previous suggestions of radiogenic He-4 recoil and He-3 deficits. Furthermore, noble gases in the Ni-Fe show evidence for in situ produced radiogenic He-4 and in some cases for recoil loss of Ar-38 and gain of Ne-21. The ratio of spallogenic Ar-38 and Ne-21 in the metal phase is found to correlate strongly with He-3/Ne-21 and Ne-22/Ne-21 in bulk samples of these chondrites. This is proof of the dependence of these ratios on the irradiation hardness experienced by the meteoroid in space. 'Hardness indices' n equals 1.9-2.2 are found, indicating that on the average the stone meteoroids from which the samples came were smaller in mass than iron meteoroids. The spallogenic Ne-21/Ar-38 ratio in metallic Ni-Fe can be used with the semi-empirical production model deduced from the Grant iron meteorite to calibrate spallogenic He-3/Ne-21 and Ne-21/Ar-38 in bulk samples of L, LL and H chondrites for meteoroid size and sample location allowing the estimation of minimal meteoroid masses.

  3. The biosynthetic routes for carbon monoxide and cyanide in the Ni-Fe active site of hydrogenases are different.

    PubMed

    Roseboom, Winfried; Blokesch, Melanie; Böck, August; Albracht, Simon P J

    2005-01-17

    The incorporation of carbon into the carbon monoxide and cyanide ligands of [NiFe]-hydrogenases has been investigated by using (13)C labelling in infrared studies of the Allochromatium vinosum enzyme and by (14)C labelling experiments with overproduced Hyp proteins from Escherichia coli. The results suggest that the biosynthetic routes of the carbon monoxide and cyanide ligands in [NiFe]-hydrogenases are different.

  4. Magnetic and electrical characterization of nickel-rich NiFe thin films synthesized by atomic layer deposition and subsequent thermal reduction

    NASA Astrophysics Data System (ADS)

    Espejo, A. P.; Zierold, R.; Gooth, J.; Dendooven, J.; Detavernier, C.; Escrig, J.; Nielsch, K.

    2016-08-01

    Nickel-rich NiFe thin films (Ni92Fe8, Ni89Fe11 and Ni83Fe17) were prepared by combining atomic layer deposition (ALD) with a subsequent thermal reduction process. In order to obtain Ni x Fe1-x O y films, one ALD supercycle was performed according to the following sequence: m NiCp2/O3, with m = 1, 2 or 3, followed by one FeCp2/O3 cycle. The supercycle was repeated n times. The thermal reduction process in hydrogen atmosphere was investigated by in situ x-ray diffraction studies as a function of temperature. The metallic nickel iron alloy thin films were investigated and characterized with respect to crystallinity, morphology, resistivity, and magnetism. As proof-of-concept magnetic properties of an array of Ni83Fe17, close to the perfect Permalloy stoichiometry, nanotubes and an isolated tube were investigated.

  5. Magnetic and electrical characterization of nickel-rich NiFe thin films synthesized by atomic layer deposition and subsequent thermal reduction.

    PubMed

    Espejo, A P; Zierold, R; Gooth, J; Dendooven, J; Detavernier, C; Escrig, J; Nielsch, K

    2016-08-26

    Nickel-rich NiFe thin films (Ni92Fe8, Ni89Fe11 and Ni83Fe17) were prepared by combining atomic layer deposition (ALD) with a subsequent thermal reduction process. In order to obtain Ni x Fe1-x O y films, one ALD supercycle was performed according to the following sequence: m NiCp2/O3, with m = 1, 2 or 3, followed by one FeCp2/O3 cycle. The supercycle was repeated n times. The thermal reduction process in hydrogen atmosphere was investigated by in situ x-ray diffraction studies as a function of temperature. The metallic nickel iron alloy thin films were investigated and characterized with respect to crystallinity, morphology, resistivity, and magnetism. As proof-of-concept magnetic properties of an array of Ni83Fe17, close to the perfect Permalloy stoichiometry, nanotubes and an isolated tube were investigated. PMID:27454574

  6. Magnetic and electrical characterization of nickel-rich NiFe thin films synthesized by atomic layer deposition and subsequent thermal reduction

    NASA Astrophysics Data System (ADS)

    Espejo, A. P.; Zierold, R.; Gooth, J.; Dendooven, J.; Detavernier, C.; Escrig, J.; Nielsch, K.

    2016-08-01

    Nickel-rich NiFe thin films (Ni92Fe8, Ni89Fe11 and Ni83Fe17) were prepared by combining atomic layer deposition (ALD) with a subsequent thermal reduction process. In order to obtain Ni x Fe1‑x O y films, one ALD supercycle was performed according to the following sequence: m NiCp2/O3, with m = 1, 2 or 3, followed by one FeCp2/O3 cycle. The supercycle was repeated n times. The thermal reduction process in hydrogen atmosphere was investigated by in situ x-ray diffraction studies as a function of temperature. The metallic nickel iron alloy thin films were investigated and characterized with respect to crystallinity, morphology, resistivity, and magnetism. As proof-of-concept magnetic properties of an array of Ni83Fe17, close to the perfect Permalloy stoichiometry, nanotubes and an isolated tube were investigated.

  7. Bio-inspired fabrication of hierarchical Ni-Fe-P coated skin collagen fibers for high-performance microwave absorption.

    PubMed

    Wang, Xiaoling; Liao, Xuepin; Zhang, Wenhua; Shi, Bi

    2015-01-21

    In the present investigation, skin collagen fiber (CF) with a well defined hierarchical 3D fibrous structure was employed for the bio-inspired fabrication of high-performance microwave absorption materials. The hierarchical 3D structure of the CF was retained in the CF@Ni-Fe-P composites, and the formation of the Ni-Fe-P coating on the CF surface was identified by XRD and XPS analysis. Based on the electromagnetism parameter measurements, the maximum reflection loss (RL) of the CF@Ni-Fe-P composites reached -31.0 dB, and the width of the absorption band where reflection loss values exceeded -10.0 dB covered the whole Ku-band and some parts of the X-band (9.5-18.0 GHz). The complex permittivity and complex permeability measurements indicated that electronic loss and magnetic loss were involved in the CF@Ni-Fe-P composites for microwave absorption. In addition, due to the magnetic properties of the Ni-Fe-P coating, these CF@Ni-Fe-P composites exhibited excellent magnetic characteristics with high saturation magnetization and low coercivity values. The present investigation indicates a new possibility for the bio-matrix-based fabrication of high-performance microwave absorbing materials with lightweight and efficient absorption properties. PMID:25484199

  8. Bio-inspired fabrication of hierarchical Ni-Fe-P coated skin collagen fibers for high-performance microwave absorption.

    PubMed

    Wang, Xiaoling; Liao, Xuepin; Zhang, Wenhua; Shi, Bi

    2015-01-21

    In the present investigation, skin collagen fiber (CF) with a well defined hierarchical 3D fibrous structure was employed for the bio-inspired fabrication of high-performance microwave absorption materials. The hierarchical 3D structure of the CF was retained in the CF@Ni-Fe-P composites, and the formation of the Ni-Fe-P coating on the CF surface was identified by XRD and XPS analysis. Based on the electromagnetism parameter measurements, the maximum reflection loss (RL) of the CF@Ni-Fe-P composites reached -31.0 dB, and the width of the absorption band where reflection loss values exceeded -10.0 dB covered the whole Ku-band and some parts of the X-band (9.5-18.0 GHz). The complex permittivity and complex permeability measurements indicated that electronic loss and magnetic loss were involved in the CF@Ni-Fe-P composites for microwave absorption. In addition, due to the magnetic properties of the Ni-Fe-P coating, these CF@Ni-Fe-P composites exhibited excellent magnetic characteristics with high saturation magnetization and low coercivity values. The present investigation indicates a new possibility for the bio-matrix-based fabrication of high-performance microwave absorbing materials with lightweight and efficient absorption properties.

  9. Effect of degassing parameters on the microstructure and properties of nanocrystalline magnesium alloys in spark plasma sintering

    NASA Astrophysics Data System (ADS)

    Koo, Seong Mo; Kim, Ka Ram; Yang, Yong Suk; Kim, Hye Sung; Hwang, Dae Youn

    2016-08-01

    The spark plasma sintering (SPS) method is advantageous for sintering metallic powders due to its ability to produce a sample with fine microstructure without defects and pores even at lower temperature and within a shorter time than that produced by conventional sintering process. It is reported that a degassing treatment prior to sintering by using the SPS method was reported to be a critical step for removing particle-particle boundaries (PBs) effectively. In spite of much research on sintering processes for Mg alloys by using the SPS method, systematic studies on the effect of degassing parameters such as the degree of vacuum, degassing pressure and degassing time, on the microstructural changes and the mechanical properties are lacking. In this study, the microstructural evolution and the mechanical properties of monocrystalline Mg-6% Al alloys were investigated to determine the degassing parameters prior to sintering to remove PBs completely and to obtain a magnesium alloy having high strength and high ductility.

  10. The huge influence of nanograins on the magnetic properties of iron-based Fe Cu Nb B nanocrystalline alloys

    NASA Astrophysics Data System (ADS)

    Bremers, H.; Hupe, O.; Hofmeister, C. E.; Michele, O.; Hesse, J.

    2005-06-01

    In 1995 Skorvanek and O'Handley presented the first experimental evidence for a huge influence of nanograins on the magnetization of a nanostructured alloy. In this contribution experiments are described, performed on as-cast amorphous and nanostructured Fe79Cu1Nb7B13 alloys. In order to get nanostructured samples with different nanograin contents the samples were annealed at different properly chosen temperatures in vacuum. This led to the formation of nanograins embedded in a residual amorphous matrix. These nanograins consist of pure bcc Fe of about 5-6 nm in diameter. Their content can be enhanced without markedly changing their size when annealing at slightly higher temperatures. So an alloy series with the same nominal composition but different nanograin contents and residual amorphous matrices, i.e. a series of nanostructured alloys, was obtained. Our aim was to study the influence of increasing nanograin concentration on the magnetic properties of the coupled system amorphous matrix plus nanograins. We describe magnetization measurements over a wide temperature range, below and above the Curie temperature of the initial amorphous matrix. In a next step these measurements are evaluated in a molecular field approach assuming two different coupled ferromagnetic systems assigned to the amorphous matrix and the nanograins.

  11. One-pot synthesis of NiFe layered double hydroxide/reduced graphene oxide composite as an efficient electrocatalyst for electrochemical and photoelectrochemical water oxidation

    NASA Astrophysics Data System (ADS)

    Youn, Duck Hyun; Park, Yoon Bin; Kim, Jae Young; Magesh, Ganesan; Jang, Youn Jeong; Lee, Jae Sung

    2015-10-01

    As an efficient non-precious metal catalyst for oxygen evolution reaction (OER) in electrochemical and photoelectrochemical water splitting, NiFe layered double hydroxide (LDH)/reduced graphene oxide (NiFe/RGO) composite is synthesized by a simple solvothermal method in one-pot. NiFe LDHs are uniformly deposited on RGO layers of high electrical conductivity and large surface area. In electrochemical water splitting, NiFe/RGO shows superior OER performance compared to bare NiFe and reference IrO2 with a lower benchmark η10 value (required overpotential to drive 10 mA cm-2) of 0.245 V. Furthermore, NiFe/RGO substantially increases the performance of a hematite photoanode in photoelectrochemical water oxidation, demonstrating its potential as an OER co-catalyst for photoelectrodes.

  12. Modifying exchange-spring behavior of CoPt/NiFe bilayer by inserting a Pt or Ru spacer

    SciTech Connect

    Hsu, Jen-Hwa Tsai, C. L.; Lee, C.-M.; Saravanan, P.

    2015-05-07

    We herein explore the possibility of obtaining tunable tilted magnetic anisotropy in ordered-CoPt (5 nm)/NiFe(t{sub NiFe}) bilayers through modifying their exchange spring behavior by inserting Pt and Ru-spacers. The tuning process of tilt angle magnetization of NiFe-layer was systematically investigated by varying the Pt or Ru thickness (t{sub Pt} or t{sub Ru}) from 0 to 8 nm at different thicknesses of NiFe (t{sub NiFe} = 1.5, 4.0, and 6.0 nm). Polar magneto-optic Kerr effect (p-MOKE) studies reveal that the bilayers grown in absence of spacers exhibit almost a rectangular hysteresis loop. With the insertion of Pt-spacer, the loop becomes more and more tilted as t{sub Pt} increases; whereas, in the case of Ru-spacer, the nature of the loops is not simply changing in one direction. The estimated SQR{sub ⊥} (= θ{sub r}/θ{sub s}) values from the p-MOKE loops are found to monotonically decrease with increasing t{sub Pt} when t{sub Pt} ≦ 4 nm. In contrast, in the case of Ru-spacer, an oscillatory behavior for the SQR{sub ⊥} values is apparent when t{sub Ru} ≦ 4 nm. As a result, an oscillatory tilted angle of NiFe spin configuration was obtained in the case of Ru-spacer; while a decoupling effect was prominent for the Pt-spacer. The results of present study reveal that the insertion of Pt and Ru-spacers as an appropriate means for realizing tunable tilted magnetic anisotropy in the CoPt/NiFe exchange springs.

  13. Novel multifunctional NiFe2O4/ZnO hybrids for dye removal by adsorption, photocatalysis and magnetic separation

    NASA Astrophysics Data System (ADS)

    Zhu, Hua-Yue; Jiang, Ru; Fu, Yong-Qian; Li, Rong-Rong; Yao, Jun; Jiang, Sheng-Tao

    2016-04-01

    Novel multifunctional NiFe2O4/ZnO hybrids were prepared by a hydrothermal method and their physicochemical properties were characterized by XRD, SEM, TEM, TGA, VSM, BET and UV-vis DRS. The adsorption and photocatalytic performance of NiFe2O4/ZnO hybrids were systematically investigated using congo red as a model contaminant. With the introduction of NiFe2O4, NiFe2O4/ZnO hybrids can absorb the whole light from 300 nm to 700 nm. The adsorption capacity (221.73 mg g-1) of NiFe2O4/ZnO hybrids is higher than those of NiFe2O4, ZnO and mechanically mixed NiFe2O4/ZnO hybrids. The removal of congo red solution (20 mg L-1) by NiFe2O4/ZnO hybrids was about 94.55% under simulated solar light irradiation for 10 min. rad OH and h+ play important roles in the decolorization of congo red solution by NiFe2O4/ZnO hybrids under simulated solar light irradiation. The decolorization efficiency of congo red solution is 97.23% for the fifth time by NiFe2O4/ZnO hybrids under simulate solar light irradiation, indicating the high photostability and durability. NO3- and Cl- anions which are ubiquitous components in dye-containing wastewater have negligible influence on the effectiveness of NiFe2O4/ZnO hybrids. Moreover, the magnetic NiFe2O4/ZnO hybrids can be easily separated from the reacted solution by an external magnet.

  14. Microstructure performance and formation mechanism of laser alloying rare earth oxides modified nanocrystalline layer on TA7

    NASA Astrophysics Data System (ADS)

    Ma, Qingyu; Gao, Xun; Li, Jianquan

    2016-03-01

    Nanoscale particles (NP) were observed in a Ni60-Ag-Si3N4-Y2O3 laser alloying (LA) layer on a TA7 titanium alloy, NP usually locate on the grain boundaries, which are able to block the motion of dislocation in a certain extent. Such layer mainly consisted of γ-Ni, TiN, γ-(Fe, Ni), TiAg and lots of amorphous phases. The wear resistance of such layer with laser scanning speed 3 mm/s was better than that of a LA layer with 6 mm/s, which was mainly ascribed to an uniform microstructure and less defect of layer. The high laser scanning speed made the existing time of laser molten pool be shorter than before, favoring the formation of a fine microstructure. However, the defects, such as pores were produced in LA layer (higher scanning speed), decreasing the wear resistance.

  15. Performance of a prototype power transformer constructed by nanocrystalline Fe-Co-Si-B-P-Cu soft magnetic alloys

    NASA Astrophysics Data System (ADS)

    Takenaka, Kana; Nishiyama, Nobuyuki; Setyawan, Albertus D.; Sharma, Parmanand; Makino, Akihiro

    2015-05-01

    To clarify the feasibility and performance of Fe81.2Co4Si0.5B9.5P4Cu0.8 alloy (with trade name NANOMET®) for electrical power applications, a prototype transformer was constructed. After surface treatment, as-quenched ribbons with a constant width of 50 mm and a thickness of ˜30 μm were wound into a toroidal shape. Nanocrystallization of toroidal core was performed by immersing it in a salt at 673 K for 180 s. The transformer constructed in the present work exhibit low core loss similar to the transformer constructed by a commercial Fe-based amorphous alloy. In spite of issues related to the annealing/nano-crystallization of the core, the feasibility for commercialization of NANOMET in power transformer applications can be confirmed. We believe the potential of NANOMET as core material for next generation of power transformer seems to be huge.

  16. Characterization of atomic-level structure in Fe-based amorphous and nanocrystalline alloy by experimental and modeling methods

    SciTech Connect

    Babilas, Rafał

    2015-09-15

    The atomic structure of Fe{sub 70}Nb{sub 10}B{sub 20} alloy in “as-cast” state and after annealing was investigated using high-energy X-ray diffraction (XRD), Mössbauer spectroscopy (MS) and high resolution transmission electron microscopy (HRTEM). The HRTEM observations allowed to indicate some medium-range order (MRO) regions about 2 nm in size and formation of some kinds of short-range order (SRO) structures represented by atomic clusters with diameter ca. 0.5 nm. The Reverse Monte Carlo (RMC) method basing on the results of XRD measurements was used in modeling the atomic structure of Fe-based alloy. The structural model was described by peak values of partial pair correlation functions and coordination numbers determined by Mössbauer spectroscopy investigations. The three-dimensional configuration box of atoms was obtained from the RMC simulation and the representative Fe-centered clusters were taken from the calculated structure. According to the Gonser et al. approach, the measured spectra of alloy studied were decomposed into 5 subspectra representing average Fe–Fe coordination numbers. Basing on the results of disaccommodation of magnetic permeability, which is sensitive to the short order of the random packing of atoms, it was stated that an occurrence of free volume is not detected after nanocrystallization process. - Highlights: • Atomic cluster model of amorphous structure was proposed for studied glassy alloy. • Short range order (ca. 0.5 nm) regions interpreted as clusters were identified by HREM. • Clusters correspond to coordination numbers (N = 4,6,8,9) calculated by using Gonser approach. • Medium-range order (ca. 2 nm) could be referred to few atomic clusters. • SRO regions are able to grow up as nuclei of crystalline bcc Fe and iron borides. • Crystalline particles have spherical morphology with an average diameter of 20 nm.

  17. 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

  18. Non-local detection of spin dynamics via spin rectification effect in yttrium iron garnet/SiO{sub 2}/NiFe trilayers near simultaneous ferromagnetic resonance

    SciTech Connect

    Soh, Wee Tee Ong, C. K.; Peng, Bin

    2015-08-15

    The spin rectification effect (SRE), a phenomenon that generates dc voltages from ac microwave fields incident onto a conducting ferromagnet, has attracted widespread attention due to its high sensitivity to ferromagnetic resonance (FMR) as well as its relevance to spintronics. Here, we report the non-local detection of yttrium iron garnet (YIG) spin dynamics by measuring SRE voltages from an adjacent conducting NiFe layer up to 200 nm thick. In particular, we detect, within the NiFe layer, SRE voltages stemming from magnetostatic surface spin waves (MSSWs) of the adjacent bulk YIG which are excited by a shorted coaxial probe. These non-local SRE voltages within the NiFe layer that originates from YIG MSSWs are present even in 200 nm-thick NiFe films with a 50 nm thick SiO{sub 2} spacer between NiFe and YIG, thus strongly ruling out the mechanism of spin-pumping induced inverse spin Hall effect in NiFe as the source of these voltages. This long-range influence of YIG dynamics is suggested to be mediated by dynamic fields generated from YIG spin precession near YIG/NiFe interface, which interacts with NiFe spins near the simultaneous resonance of both spins, to generate a non-local SRE voltage within the NiFe layer.

  19. Current-induced three-dimensional domain wall propagation in cylindrical NiFe nanowires

    NASA Astrophysics Data System (ADS)

    Wong, D. W.; Purnama, I.; Lim, G. J.; Gan, W. L.; Murapaka, C.; Lew, W. S.

    2016-04-01

    We report on the magnetization configurations in single NiFe cylindrical nanowires grown by template-assisted electrodeposition. Angular anisotropic magnetoresistance measurements reveal that a three-dimensional helical domain wall is formed naturally upon relaxation from a saturated state. Micromagnetic simulations support the helical domain wall properties and its reversal process, which involves a splitting of the clockwise and anticlockwise vortices. When a pulsed current is applied to the nanowire, the helical domain wall propagation is observed with a minimum current density needed to overcome its intrinsic pinning.

  20. Ni, Fe Co-doped ZnO nanoparticles synthesized by solution combustion method

    SciTech Connect

    Dhiman, Pooja Chand, Jagdish Verma, S. Sarveena, Singh, M.

    2014-04-24

    This paper outlines the synthesis and characterization of Ni-Fe co-doped ZnO nanoparticles by facile solution combustion method. The structural characterization by XRD confirmed the phase purity of the samples. Surface morphology studied by scanning electron microscope revealed cubic type shape of grains. EDS analysis conformed the elemental composition. Higher value of DC electrical conductivity and less band gap for co-doped ZnO from UV-Vis studies confirmed the change in defect chemistry of ZnO Matrix.

  1. Effect of biquadratic coupling on current induced magnetization switching in Co/Cu/Ni-Fe nanopillar

    NASA Astrophysics Data System (ADS)

    Aravinthan, D.; Sabareesan, P.; Daniel, M.

    2016-05-01

    The effect of biquadratic coupling on spin current induced magnetization switching in a Co/Cu/Ni-Fe nanopillar device is investigated by solving the free layer magnetization switching dynamics governed by the Landau-Lifshitz-Gilbert-Slonczewski (LLGS) equation. The LLGS equation is numerically solved by using Runge-Kutta fourth order procedure for an applied current density of 5 × 1012 Am-2. Presence of biquadratic coupling in the ferromagnetic layers reduces the magnetization switching time of the nanopillar device from 61 ps to 49 ps.

  2. Concerto catalysis--harmonising [NiFe]hydrogenase and NiRu model catalysts.

    PubMed

    Ichikawa, Koji; Nonaka, Kyoshiro; Matsumoto, Takahiro; Kure, Bunsho; Yoon, Ki-Seok; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

    2010-03-28

    This communication reports the successful merging of the chemical properties of a natural [NiFe]hydrogenase (Desulfovibrio vulgaris Miyazaki F) and our previously reported [NiRu] hydrogenase-mimic. The catalytic activity of both the natural enzyme and the mimic is almost identical, with the exception of working pH ranges, and this allows us to use them simultaneously in the same reaction flask. In such a manner, isotope exchange between D(2) and H(2)O could be conducted over an extended pH range (about 2-10) in one pot under mild conditions at ambient temperature and pressure.

  3. Kinetics and thermodynamics of gas diffusion in a NiFe hydrogenase.

    PubMed

    Topin, Jérémie; Rousset, Marc; Antonczak, Serge; Golebiowski, Jérôme

    2012-03-01

    We have investigated O₂ and H₂ transport across a NiFe hydrogenase at the atomic scale by means of computational methods. The Wild Type protein has been compared with the V74Q mutant. Two distinct methodologies have been applied to study the gas access to the active site. Temperature locally enhanced sampling simulations have emphasized the importance of protein dynamics on gas diffusion. The O₂ diffusion free energy profiles, obtained by umbrella sampling, are in agreement with the known kinetic data and show that in the V74Q mutant, the inhibition process is lowered from both a kinetic and a thermodynamic point of view.

  4. Gas phase hydrogen permeation in a Ni-Fe-Co superalloy

    NASA Technical Reports Server (NTRS)

    Shanabarger, Mickey R.

    1993-01-01

    Hydrogen permeation measurements have been conducted for the Incoloy 909 Ni-Fe-Co superalloy via the 'membrane' technique, in which the gaseous hydrogen at the entrance of a thin membrane is transposed through the bulk to the exit side of the membrane, at 400-810 C; the pressure range explored was 2.7 x 10 exp 3 to 1.3 x 10 exp 5 N/sq m. The lattice hydrogen solubility of Incoloy 909 is found to be only weakly temperature-dependent. These results are compared with those obtained for Incoloy 903.

  5. The effect of solution pH on the electrochemical performance of nanocrystalline metal ferrites MFe2O4 (M=Cu, Zn, and Ni) thin films

    NASA Astrophysics Data System (ADS)

    Elsayed, E. M.; Rashad, M. M.; Khalil, H. F. Y.; Ibrahim, I. A.; Hussein, M. R.; El-Sabbah, M. M. B.

    2016-04-01

    Nanocrystalline metal ferrite MFe2O4 (M=Cu, Zn, and Ni) thin films have been synthesized via electrodeposition-anodization process. Electrodeposited (M)Fe2 alloys were obtained from aqueous sulfate bath. The formed alloys were electrochemically oxidized (anodized) in aqueous (1 M KOH) solution, at room temperature, to the corresponding hydroxides. The parameters controlling the current efficiency of the electrodeposition of (M)Fe2 alloys such as the bath composition and the current density were studied and optimized. The anodized (M)Fe2 alloy films were annealed in air at 400 °C for 2 h. The results revealed the formation of three ferrite thin films were formed. The crystallite sizes of the produced films were in the range between 45 and 60 nm. The microstructure of the formed film was ferrite type dependent. The corrosion behavior of ferrite thin films in different pH solutions was investigated using open circuit potential (OCP) and potentiodynamic polarization measurements. The open circuit potential indicates that the initial potential E im of ZnFe2O4 thin films remained constant for a short time, then sharply increased in the less negative direction in acidic and alkaline medium compared with Ni and Cu ferrite films. The values of the corrosion current density I corr were higher for the ZnFe2O4 films at pH values of 1 and 12 compared with that of NiFe2O4 and CuFe2O4 which were higher only at pH value 1. The corrosion rate was very low for the three ferrite films when immersion in the neutral medium. The surface morphology recommended that Ni and Cu ferrite films were safely used in neutral and alkaline medium, whereas Zn ferrite film was only used in neutral atmospheres.

  6. Characterization of Ni-Fe/Si{sub 3}N{sub 4} Nanocomposite Coatings Deposited by Electroplating

    SciTech Connect

    Marita, Yusrini; Yaacob, Iskandar Idris

    2009-05-27

    Ni-Fe/Si{sub 3}N{sub 4} nanocomposite coatings with various amount of Si{sub 3}N{sub 4} were prepared by electrodeposition technique. The effect of Si{sub 3}N{sub 4} nanoparticulates in the Ni-Fe nanocomposite coatings was investigated in relation to the ratio of Si{sub 3}N{sub 4} to Na-saccharine in the plating bath. X-ray diffraction analysis showed that the Ni-Fe nanocomposite coating has face-centered cubic structure (FCC). However, a mixture of body-centered cubic (BCC) and face-centered cubic (FCC) phases was observed when the ratio of Si{sub 3}N{sub 4} to Na-saccharine was around 8.3. The crystallite size of the Ni-Fe nanocomposite coating decreased when the ratio of Si{sub 3}N{sub 4} to Na-saccharine was increased. From the results of the elemental mapping procedure, it was found that inclusions of silicon were uniformly distributed in Ni-Fe composite coating, indicating good dispersion of Si{sub 3}N{sub 4} and this contributed in increasing the microhardness of coating.

  7. Genetic diversity and expression of the [NiFe] hydrogenase large-subunit gene of Desulfovibrio spp. in environmental samples.

    PubMed Central

    Wawer, C; Jetten, M S; Muyzer, G

    1997-01-01

    The genetic diversity and expression of the [NiFe] hydrogenase large-subunit gene of Desulfovibrio spp. in environmental samples were determined in order to show in parallel the existing and active members of Desulfovibrio populations. DNA and total RNA were extracted from different anaerobic bioreactor samples; RNA was transcribed into cDNA. Subsequently, PCR was performed to amplify a ca.-440-bp fragment of the [NiFe] hydrogenase large-subunit gene and its mRNA. Denaturing gradient gel electrophoresis analysis was used to separate the PCR products according to their sequence and thereby to visualize the individual community members. Desulfovibrio strains corresponding to amplified [NiFe] hydrogenase transcripts were regarded as metabolically active, because in pure cultures transcripts were detectable in exponentially growing cells but not in cultures in the stationary phase. DNA sequencing and comparative sequence analysis were used to identify the detected organisms on the basis of their [NiFe] hydrogenase sequences. The genes of characterized Desulfovibrio spp. showed a considerable extent of divergence (ca. 30%), whereas sequences obtained from bacterial populations of the bioreactors showed a low level of variation and indicated the coexistence of closely related strains probably belonging to the species Desulfovibrio sulfodismutans. Under methanogenic conditions, all detected populations were active; under denitrifying conditions, no [NiFe] hydrogenase mRNA was visible. Changes in activity and composition of Desulfovibrio populations caused by changes in the environmental conditions could be monitored by using the approach described in this study. PMID:9361423

  8. A flexible alkaline rechargeable Ni/Fe battery based on graphene foam/carbon nanotubes hybrid film.

    PubMed

    Liu, Jilei; Chen, Minghua; Zhang, Lili; Jiang, Jian; Yan, Jiaxu; Huang, Yizhong; Lin, Jianyi; Fan, Hong Jin; Shen, Ze Xiang

    2014-12-10

    The development of portable and wearable electronics has promoted increasing demand for high-performance power sources with high energy/power density, low cost, lightweight, as well as ultrathin and flexible features. Here, a new type of flexible Ni/Fe cell is designed and fabricated by employing Ni(OH)2 nanosheets and porous Fe2O3 nanorods grown on lightweight graphene foam (GF)/carbon nanotubes (CNTs) hybrid films as electrodes. The assembled f-Ni/Fe cells are able to deliver high energy/power densities (100.7 Wh/kg at 287 W/kg and 70.9 Wh/kg at 1.4 kW/kg, based on the total mass of active materials) and outstanding cycling stabilities (retention 89.1% after 1000 charge/discharge cycles). Benefiting from the use of ultralight and thin GF/CNTs hybrid films as current collectors, our f-Ni/Fe cell can exhibit a volumetric energy density of 16.6 Wh/l (based on the total volume of full cell), which is comparable to that of thin film battery and better than that of typical commercial supercapacitors. Moreover, the f-Ni/Fe cells can retain the electrochemical performance with repeated bendings. These features endow our f-Ni/Fe cells a highly promising candidate for next generation flexible energy storage systems.

  9. The influence of an MgO nanolayer on the planar Hall effect in NiFe films

    SciTech Connect

    Li, Minghua; Zhao, Zhiduo; Ma, Lin; Lu, Xiangan; Teng, Jiao; Yu, Guanghua; Yu, Guoqiang; Amiri, Pedram Khalili; Wang, Kang L.; Zhou, Wenping

    2015-03-28

    The Planar Hall Effect (PHE) in NiFe films was studied using MgO as the buffer and capping layer to reduce the shunt effect. The thermal annealing was found to be effective in increasing the sensitivity. The sensitivity of the magnetic field reached as high as 865 V/AT in a MgO (3 nm)/NiFe (5 nm)/MgO(3 nm)/Ta(3 nm) structure after annealing at 500 °C for 2 h, which is close to the sensitivity of semiconductor Hall Effect (HE) sensors. X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) were used to study the sample. The results show that the top crystallization of MgO and NiFe (111) texture were improved by proper annealing. The smooth and clear bottom MgO/NiFe and top NiFe/MgO interface is evident from our data. In addition, the shunt current of Ta was decreased. These combined factors facilitate the improvement of the sensitivity of the magnetic field.

  10. Influence of metallurgical parameters on the electrochemical behavior of electrodeposited Ni and Ni-W nanocrystalline alloys

    NASA Astrophysics Data System (ADS)

    Shakibi Nia, N.; Creus, J.; Feaugas, X.; Savall, C.

    2016-05-01

    The electrochemical behavior of electrodeposited nickel and Ni-W nanostructured alloys is discussed by studying the polarization curves in acidic medium. As tungsten content varies, several metallurgical parameters that can influence the electrochemical behavior are also modified, namely grain size, nature of grain boundaries, crystallographic texture and light element contamination. Comparing the behavior of Ni-W coatings with that of pure nickel and annealed coatings highlights that tungsten incorporation enhances anodic dissolution and has a detrimental influence on passive film, whereas grain size and grain boundary character behave as second-order parameters.

  11. Self-assembled NiFe2O4/carbon nanotubes sponge for enhanced glucose biosensing application

    NASA Astrophysics Data System (ADS)

    Li, Yingchun; Zhao, Minggang; Chen, Jing; Fan, Sisi; Liang, Jingjing; Ding, Longjiang; Chen, Shougang

    2016-01-01

    In this work, self-assembled NiFe2O4/carbon nanotubes (CNTs) sponge was prepared by ice-templating method. The device synergized the advantageous features of both the 3D porous nanostructure and the catalytic properties of CNTs with GOx and NiFe2O4 nanoparticles. The porous network construction of the NiFe2O4/CNTs sheets offered enlarged specific surface for GOx immobilization and opened channels for facilitating the electrons transport and reactants diffusion. With the help of the abnormal-valence elements Ni and Fe, double catalysis has happened and the enhanced glucose biosensing performance has been achieved. The fabricated glucose biosensor exhibited two large linear ranges (0-3.0 and 3.2-12.4 mM) and distinct sensitivities (84.1 and 24.6 μA mM-1 cm-2).

  12. Hydride bridge in [NiFe]-hydrogenase observed by nuclear resonance vibrational spectroscopy

    SciTech Connect

    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; Lubitz, Wolfgang; Cramer, Stephen P.

    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 a 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.

  13. Hydride bridge in [NiFe]-hydrogenase observed by nuclear resonance vibrational spectroscopy

    NASA Astrophysics Data System (ADS)

    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.

    2015-08-01

    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.

  14. Synthesis and magnetic properties of NiFe2-xSmxO4 nanopowder

    NASA Astrophysics Data System (ADS)

    Hassanzadeh-Tabrizi, S. A.; Behbahanian, Shahrzad; Amighian, Jamshid

    2016-07-01

    NiFe2-xSmxO4 (x=0.00, 0.05, 0.10 and 0.15) nanopowders were synthesized via a sol-gel combustion route. The structural studies were carried out by X-ray diffractometer, Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. The XRD results confirmed the formation of single-phase spinel cubic structure. The crystallite size decreased with an increase of samarium ion concentration, while lattice parameter and lattice strain increased with samarium substitution. TEM micrographs showed that agglomerated nanoparticles with particle sizes ranging from 35 to 90 nm were obtained. The magnetic studies were carried out using vibrating sample magnetometer. Magnetic measurements revealed that the saturation magnetization (Ms) of NiFe2-xSmxO4 nanoparticles decreases with increasing Sm3+substitution. The reduction of saturation magnetization is attributed to the dilution of the magnetic interaction. The coercivity (Hc) of samples increases by adding samarium.

  15. A functional [NiFe]-hydrogenase model compound that undergoes biologically relevant reversible thiolate protonation.

    PubMed

    Weber, Katharina; Krämer, Tobias; Shafaat, Hannah S; Weyhermüller, Thomas; Bill, Eckhard; van Gastel, Maurice; Neese, Frank; Lubitz, Wolfgang

    2012-12-26

    Two model compounds of the active site of [NiFe]-hydrogenases with an unusual {S(2)Ni(μ-S)(μ-CO)Fe(CO)(2)S}-coordination environment around the metals are reported. The neutral compound [Ni(xbsms)(μ-CO)(μ-S)Fe(CO)(2)('S')], (1) (H(2)xbsms = 1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene) is converted to [1H][BF(4)] by reversible protonation using HBF(4)·Et(2)O. The protonation takes place at the terminal thiolate sulfur atom that is coordinated to nickel. Catalytic intermediates with a protonated terminal cysteinate were suggested for the native protein but have not yet been confirmed experimentally. [1H][BF(4)] is the first dinuclear [NiFe] model compound for such a species. Both complexes have been synthesized and characterized by X-ray crystallography, NMR-, FTIR-, and (57)Fe-Mössbauer spectroscopy as well as by electronic absorption and resonance Raman spectroscopy. The experimental results clearly show that the protonation has a significant impact on the electronic structure of the iron center, although it takes place at the nickel site. DFT calculations support the interpretation of the spectroscopic data and indicate the presence of a bonding interaction between the metal ions, which is relevant for the enzyme as well. Electrochemical experiments show that both 1 and [1H][BF(4)] are active for electrocatalytic proton reduction in aprotic solvents.

  16. 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

  17. A functional [NiFe]-hydrogenase model compound that undergoes biologically relevant reversible thiolate protonation.

    PubMed

    Weber, Katharina; Krämer, Tobias; Shafaat, Hannah S; Weyhermüller, Thomas; Bill, Eckhard; van Gastel, Maurice; Neese, Frank; Lubitz, Wolfgang

    2012-12-26

    Two model compounds of the active site of [NiFe]-hydrogenases with an unusual {S(2)Ni(μ-S)(μ-CO)Fe(CO)(2)S}-coordination environment around the metals are reported. The neutral compound [Ni(xbsms)(μ-CO)(μ-S)Fe(CO)(2)('S')], (1) (H(2)xbsms = 1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene) is converted to [1H][BF(4)] by reversible protonation using HBF(4)·Et(2)O. The protonation takes place at the terminal thiolate sulfur atom that is coordinated to nickel. Catalytic intermediates with a protonated terminal cysteinate were suggested for the native protein but have not yet been confirmed experimentally. [1H][BF(4)] is the first dinuclear [NiFe] model compound for such a species. Both complexes have been synthesized and characterized by X-ray crystallography, NMR-, FTIR-, and (57)Fe-Mössbauer spectroscopy as well as by electronic absorption and resonance Raman spectroscopy. The experimental results clearly show that the protonation has a significant impact on the electronic structure of the iron center, although it takes place at the nickel site. DFT calculations support the interpretation of the spectroscopic data and indicate the presence of a bonding interaction between the metal ions, which is relevant for the enzyme as well. Electrochemical experiments show that both 1 and [1H][BF(4)] are active for electrocatalytic proton reduction in aprotic solvents. PMID:23194246

  18. Proton-coupled electron transfer dynamics in the catalytic mechanism of a [NiFe]-hydrogenase.

    PubMed

    Greene, Brandon L; Wu, Chang-Hao; McTernan, Patrick M; Adams, Michael W W; Dyer, R Brian

    2015-04-01

    The movement of protons and electrons is common to the synthesis of all chemical fuels such as H2. Hydrogenases, which catalyze the reversible reduction of protons, necessitate transport and reactivity between protons and electrons, but a detailed mechanism has thus far been elusive. Here, we use a phototriggered chemical potential jump method to rapidly initiate the proton reduction activity of a [NiFe] hydrogenase. Coupling the photochemical initiation approach to nanosecond transient infrared and visible absorbance spectroscopy afforded direct observation of interfacial electron transfer and active site chemistry. Tuning of intramolecular proton transport by pH and isotopic substitution revealed distinct concerted and stepwise proton-coupled electron transfer mechanisms in catalysis. The observed heterogeneity in the two sequential proton-associated reduction processes suggests a highly engineered protein environment modulating catalysis and implicates three new reaction intermediates; Nia-I, Nia-D, and Nia-SR(-). The results establish an elementary mechanistic understanding of catalysis in a [NiFe] hydrogenase with implications in enzymatic proton-coupled electron transfer and biomimetic catalyst design.

  19. Structure evolution, magnetic properties and giant magnetoresistance of granular NiFeCo-Ag films

    NASA Astrophysics Data System (ADS)

    Wang, Hao; Wong, S. P.; Lu, Xiang; Yan, Xin; Cheung, W. Y.; Ke, N.; Hu, Shejun; Zeng, Dechang; Liu, Zhenyi

    2000-06-01

    The structure evolution of granular (NiFeCo)xAg(1-x) (x = 9-41 at%) films was characterized by x-ray photoelectron spectroscopy, Rutherford backscattering spectroscopy, x-ray diffraction, atomic force microscopy and magnetic force microscopy. The giant magnetoresistance of the films was measured as a function of temperature between 20 and 300 K using a conventional four-point probe dc technique in the presence of a magnetic field up to 7.6 kOe. The temperature dependence of magnetization and magnetic hysteresis loops for the films were measured by a SQUID magnetometer. It was found that the optimum concentration and annealing temperature for the maximum giant magnetoresistance was associated with the crystalline structure and the magnetic domain structure of the film. A clear flat-top parabola and a significant deviation from the quadratic law expected for equal-size, non-interacting superparamagnetic particles in the magnetoresistance (Δρ/ρ) against magnetization (M/Ms) curve were observed for the 500 °C annealed (NiFeCo)20Ag80 sample in a wide field region. The curves of Δρ/ρ against M/Ms were well described by a function of the form c(M/Ms)10. This behaviour was explained by combining the characteristics of the microstructure, magnetic domain structure and magnetic properties of the sample.

  20. Supersolar Ni/Fe production in the Type IIP SN 2012ec

    NASA Astrophysics Data System (ADS)

    Jerkstrand, A.; Smartt, S. J.; Sollerman, J.; Inserra, C.; Fraser, M.; Spyromilio, J.; Fransson, C.; Chen, T.-W.; Barbarino, C.; Dall'Ora, M.; Botticella, M. T.; Della Valle, M.; Gal-Yam, A.; Valenti, S.; Maguire, K.; Mazzali, P.; Tomasella, L.

    2015-04-01

    SN 2012ec is a Type IIP supernova (SN) with a progenitor detection and comprehensive photospheric phase observational coverage. Here, we present Very Large Telescope and Public ESO Spectroscopic Survey of Transient Objects observations of this SN in the nebular phase. We model the nebular [O I] λλ6300, 6364 lines and find their strength to suggest a progenitor main-sequence mass of 13-15 M⊙. SN 2012ec is unique among hydrogen-rich SNe in showing a distinct line of stable nickel [Ni II] λ7378. This line is produced by 58Ni, a nuclear burning ash whose abundance is a sensitive tracer of explosive burning conditions. Using spectral synthesis modelling, we use the relative strengths of [Ni II] λ7378 and [Fe II] λ7155 (the progenitor of which is 56Ni) to derive a Ni/Fe production ratio of 0.20 ± 0.07 (by mass), which is a factor 3.4 ± 1.2 times the solar value. High production of stable nickel is confirmed by a strong [Ni II] 1.939 μm line. This is the third reported case of a core-collapse SN producing a Ni/Fe ratio far above the solar value, which has implications for core-collapse explosion theory and galactic chemical evolution models.

  1. Hydride bridge in [NiFe]-hydrogenase observed by nuclear resonance vibrational spectroscopy

    DOE PAGESBeta

    Ogata, Hideaki; Krämer, Tobias; Wang, Hongxin; Schilter, David; Pelmenschikov, Vladimir; van Gastel, Maurice; Neese, Frank; Rauchfuss, Thomas B.; Gee, Leland B.; Scott, Aubrey D.; et al

    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

  2. Atomically thin layered NiFe double hydroxides assembled 3D microspheres with promoted electrochemical performances

    NASA Astrophysics Data System (ADS)

    Li, Xiaomin; Zai, Jiantao; Liu, Yuanyuan; He, Xiaobo; Xiang, Shijie; Ma, Zifeng; Qian, Xuefeng

    2016-09-01

    LDHs in atomic thickness (mono-/bi-layers) usually exhibit novel physicochemical properties, especially in surface-dependent energy storage and catalysis areas. However, the thickness of the commonly reported 2D LDHs is in nanoscale and the bottom-up synthesis of atomically thin LDHs is rarely reported. Herein, high-quality atomically thin layered NiFe-LDHs assembled 3D microspheres were synthesized via a rational designed reaction system, where the formation of atomically thin building blocks was controlled by the synergetic effects of released carbonate anions and butanol. Furthermore, the complexant and solvents played important effects on the process of coprecipitation and the assembling of LDHs. Due to the nature of atomically thin LDHs nanosheets and unique 3D hierarchical structures, the obtained microspheres exhibited excellent electrocatalytic oxygen evolution reaction (OER) activity in alkaline medium with an onset overpotential (0.435 V, which is lower than that of common LDHs) and good durability. The as-prepared 3D NiFe-LDHs microspheres were also firstly used as supercapacitor materials and displayed a high specific capacitance of 1061 F g-1 at the current density of 1 A g-1.

  3. Reversible [4Fe-3S] cluster morphing in an O(2)-tolerant [NiFe] hydrogenase.

    PubMed

    Frielingsdorf, Stefan; Fritsch, Johannes; Schmidt, Andrea; Hammer, Mathias; Löwenstein, Julia; Siebert, Elisabeth; Pelmenschikov, Vladimir; Jaenicke, Tina; Kalms, Jacqueline; Rippers, Yvonne; Lendzian, Friedhelm; Zebger, Ingo; Teutloff, Christian; Kaupp, Martin; Bittl, Robert; Hildebrandt, Peter; Friedrich, Bärbel; Lenz, Oliver; Scheerer, Patrick

    2014-05-01

    Hydrogenases catalyze the reversible oxidation of H(2) into protons and electrons and are usually readily inactivated by O(2). However, a subgroup of the [NiFe] hydrogenases, including the membrane-bound [NiFe] hydrogenase from Ralstonia eutropha, has evolved remarkable tolerance toward O(2) that enables their host organisms to utilize H(2) as an energy source at high O(2). This feature is crucially based on a unique six cysteine-coordinated [4Fe-3S] cluster located close to the catalytic center, whose properties were investigated in this study using a multidisciplinary approach. The [4Fe-3S] cluster undergoes redox-dependent reversible transformations, namely iron swapping between a sulfide and a peptide amide N. Moreover, our investigations unraveled the redox-dependent and reversible occurence of an oxygen ligand located at a different iron. This ligand is hydrogen bonded to a conserved histidine that is essential for H(2) oxidation at high O(2). We propose that these transformations, reminiscent of those of the P-cluster of nitrogenase, enable the consecutive transfer of two electrons within a physiological potential range. PMID:24705592

  4. Synthesis and Photophysical Study of a [NiFe] Hydrogenase Biomimetic Compound Covalently Linked to a Re-diimine Photosensitizer

    PubMed Central

    2015-01-01

    The synthesis, photophysics, and photochemistry of a linked dyad ([Re]-[NiFe2]) containing an analogue ([NiFe2]) of the active site of [NiFe] hydrogenase, covalently bound to a Re-diimine photosensitizer ([Re]), are described. Following excitation, the mechanisms of electron transfer involving the [Re] and [NiFe2] centers and the resulting decomposition were investigated. Excitation of the [Re] center results in the population of a diimine-based metal-to-ligand charge transfer excited state. Reductive quenching by NEt3 produces the radically reduced form of [Re], [Re]− (kq = 1.4 ± 0.1 × 107 M–1 s–1). Once formed, [Re]− reduces the [NiFe2] center to [NiFe2]−, and this reduction was followed using time-resolved infrared spectroscopy. The concentration dependence of the electron transfer rate constants suggests that both inter- and intramolecular electron transfer pathways are involved, and the rate constants for these processes have been estimated (kinter = 5.9 ± 0.7 × 108 M–1 s–1, kintra = 1.5 ± 0.1 × 105 s–1). For the analogous bimolecular system, only intermolecular electron transfer could be observed (kinter = 3.8 ± 0.5 × 109 M–1 s–1). Fourier transform infrared spectroscopic studies confirms that decomposition of the dyad occurs upon prolonged photolysis, and this appears to be a major factor for the low activity of the system toward H2 production in acidic conditions. PMID:26605700

  5. Effect of Heating Rate on Soft Magnetic Properties in Nanocrystalline Fe80.5Cu1.5Si4B14 and Fe82Cu1Nb1Si4B12 Alloys

    NASA Astrophysics Data System (ADS)

    Ohta, Motoki; Yoshizawa, Yoshihito

    2009-02-01

    The effect of the heating rate in the annealing process of rapidly quenched Fe80.5Cu1.5Si4B14 and Fe82Cu1Nb1Si4B12 amorphous alloys on their soft magnetic properties is investigated. The iron loss in magnetic flux density region of B > 1.55 T in Fe80.5Cu1.5Si4B14 alloy decreases by high-heating-rate annealing (HA). The coercivity Hc and the saturation magnetic flux density Bs in HA specimen of Fe82Cu1Nb1Si4B12 alloy were about 3 A/m and 1.78 T. By applying HA to high-Fe-concentration amorphous alloys such as Fe82Cu1Nb1Si4B12, Fe82Cu1Nb1Si2B12P2, and Fe80.8Cu1.2Si5B11P2, the nanocrystalline alloys with a high Bs of more than 1.75 T and a low Hc of about 3 A/m are obtained.

  6. Ferromagnetic resonance study of the misalignment between anisotropy axes in exchange-biased NiFe/FeMn/Co trilayers

    NASA Astrophysics Data System (ADS)

    Barreto, P. G.; Sousa, M. A.; Pelegrini, F.; Alayo, W.; Litterst, F. J.; Baggio-Saitovitch, E.

    2014-05-01

    Exchange-biased NiFe/FeMn/Co trilayers were grown by dc magnetron sputtering and analyzed by in-plane ferromagnetic resonance using Q-band microwaves. The experiments revealed that distinct Co and NiFe resonance modes were excited by the microwave field. A misalignment between the anisotropy axes of the magnetic layers was deduced from the angular variations of the resonance fields, which also showed the effects of uniaxial and unidirectional anisotropies. A phenomenological model was used to fit the experimental results taking also into account a rotatable anisotropy field associated to the domain structure of the FeMn layer and the magnetic history of the films.

  7. High Temperature Stable Nanocrystalline SiGe Thermoelectric Material

    NASA Technical Reports Server (NTRS)

    Yang, Sherwin (Inventor); Matejczyk, Daniel Edward (Inventor); Determan, William (Inventor)

    2013-01-01

    A method of forming a nanocomposite thermoelectric material having microstructural stability at temperatures greater than 1000 C. The method includes creating nanocrystalline powder by cryomilling. The method is particularly useful in forming SiGe alloy powder.

  8. Achieving Superior Two-Way Actuation by the Stress-Coupling of Nanoribbons and Nanocrystalline Shape Memory Alloy.

    PubMed

    Hao, Shijie; Liu, Yinong; Ren, Yang; Jiang, Daqiang; Yang, Feng; Cong, Daoyong; Wang, Yandong; Cui, Lishan

    2016-06-29

    Inspired by the driving principle of traditional bias-type two-way actuators, we developed a novel two-way actuation nanocomposite wire in which a massive number of Nb nanoribbons with ultralarge elastic strains are loaded inside a shape memory alloy (SMA) matrix to form a continuous array of nanobias actuation pairs for two-way actuation. The composite exhibits a two-way actuation strain of 3.2% during a thermal cycle and an actuation stress of 934 MPa upon heating, which is about twice as high as that (∼500 MPa) found in reported two-way SMAs. Upon cooling, the composite shows an actuation stress of 134 MPa and a mechanical work output of 1.08 × 10(6) J/m(3), which are about three and five times higher than those of reported two-way SMAs, respectively. It was revealed that the massive number of Nb nanoribbons in the compressive state provides the high actuation stress and high work output upon cooling, and the SMA matrix with high yield strength offers the high actuation stress upon heating. Compared to traditional bias-type two-way actuators, the two-way actuation composite with a small volume and simple construct works well with the miniaturization and simplification of actuators. PMID:27276656

  9. Comparison of microwave absorption properties of SrFe12O19, SrFe12O19/NiFe2O4, and NiFe2O4 particles

    NASA Astrophysics Data System (ADS)

    Mehdipour, M.; Shokrollahi, H.

    2013-07-01

    In this study, ferrimagnetic (SrFe12O19, SrFe12O19/NiFe2O4, and NiFe2O4) nanostructure particles were synthesized by the co-precipitation of chloride salts using the sodium hydroxide solution. The resulting precursors were heat-treated at 1100 °C for 4 h. After cooling in the furnace, the ferrite powders were pressed at 10 bars and then sintered at 1200 °C for 4 h. The saturation magnetization was increased and the coercivity was decreased by sintering (because of morphology changing) and alternating of the ferrite kind. For example, at SrFe12O19, the saturation magnetization was increased from 291 G to 300 G and the coercivity was decreased from 2.8 kOe to 1.8 kOe by sintering. The microwave absorption properties of the nanostructure particles were studied by ferromagnetic resonance and transmit-line theories, as well as Reflection Loss plots. Before sintering, the RL spectra of SrFe12O19 and the composite were below -3 dB, but they reached -6 dB at 11.1 GHz for NiFe2O4. The RL spectra of the samples were increased by sintering due to reduction of porosity and damping factor. The maximum microwave absorption reached -35 dB (at resonance frequency) for the NiFe2O4 state.

  10. Nanocrystalline diamond thin films on titanium-6 aluminum-4 vanadium alloy temporomandibular joint prosthesis simulants by microwave plasma chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Fries, Marc Douglas

    A course of research has been performed to assess the suitability of nanocrystal-line diamond (NCD) films on Ti-6Al-4V alloy as wear-resistant coatings in biomedical implant use. A series of temporomandibular (TMJ) joint condyle simulants were polished and acid-passivated as per ASTM F86 standard for surface preparation of implants. A 3-mum-thick coating of NCD film was deposited by microwave plasma chemical vapor deposition (MPCVD) over the hemispherical articulation surfaces of the simulants. Plasma chemistry conditions were measured and monitored by optical emission spectroscopy (OES), using hydrogen as a relative standard. The films consist of diamond grains around 20 nm in diameter embedded in an amorphous carbon matrix, free of any detectable film stress gradient. Hardness averages 65 GPa and modulus measures 600 GPa at a depth of 250 nm into the film surface. A diffuse film/substrate boundary produces a minimal film adhesion toughness (GammaC) of 158 J/m2. The mean RMS roughness is 14.6 +/- 4.2 nm, with an average peak roughness of 82.6 +/- 65.9 nm. Examination of the surface morphology reveals a porous, dendritic surface. Wear testing resulted in two failed condylar coatings out of three tests. No macroscopic delamination was found on any sample, but micron-scale film pieces broke away, exposing the substrate. Electrochemical corrosion testing shows a seven-fold reduction in corrosion rate with the application of an NCD coating as opposed to polished, passivated Ti-6Al-4V, producing a corrosion rate comparable to wrought Co-Cr-Mo. In vivo biocompatibility testing indicates that implanted NCD films did not elicit an immune response in the rabbit model, and osteointegration was apparent for both compact and trabecular bone on both NCD film and bare Ti-6Al-4V. Overall, NCD thin film material is reasonably smooth, biocompatible, and very well adhered. Wear testing indicates that this material is unacceptable for use in demanding TMJ applications without

  11. NiFe2O4 Spinel Protection Coating for High-Temperature Solid Oxide Fuel Cell Interconnect Application

    NASA Astrophysics Data System (ADS)

    Irankhah, Reza; Raissi, Babak; Maghsoudipour, Amir; Irankhah, Abdullah; Ghashghai, Sasan

    2016-04-01

    In the present study, Ni-Fe spinel powder was synthesized via a solid state reaction. In the next step, the electrophoretic deposition (EPD) method was used to apply the NiFe2O4 spinel, as an oxidation-resistant layer, on a commercially available stainless steel (SUS 430) in a potential range of 100 to 300 V. Microscopic studies of the deposited layers showed that crack-free NiFe2O4 films were obtained at 100 V. The coated and uncoated samples were then pre-sintered in air and 5% H2 bal Ar atmospheres at 900 °C for 3 h followed by cyclic oxidation at 800 °C for 500 h. The investigation of the oxidation resistance of the samples using Energy Dispersive Spectroscopy (EDS) revealed that the NiFe2O4 coating acted as an effective barrier against chromium migration into the coating. The oxidation resistance of 5% H2 bal Ar pre-sintered sample was enhanced with an oxidation rate constant ( K P) of 8.9 × 10-15 g2 cm-4 s-1.

  12. Structure of an Actinobacterial-Type [NiFe]-Hydrogenase Reveals Insight into O2-Tolerant H2 Oxidation.

    PubMed

    Schäfer, Caspar; Bommer, Martin; Hennig, Sandra E; Jeoung, Jae-Hun; Dobbek, Holger; Lenz, Oliver

    2016-02-01

    A novel group of bacterial [NiFe]-hydrogenases is responsible for high-affinity H2 uptake from the troposphere, and is therefore thought to play an important role in the global H2 cycle. Here we present the first crystal structure at 2.85-Å resolution of such an actinobacterial-type hydrogenase (AH), which was isolated from the dihydrogen oxidizing bacterium, Ralstonia eutropha. The enzyme has a dimeric structure carrying two active [NiFe] sites that are interconnected by six [4Fe4S] clusters over a range of approximately 90 Å. Unlike most other [NiFe]-hydrogenases, the [4Fe4S] cluster proximal to the [NiFe] site is coordinated by three cysteines and one aspartate. Mutagenesis experiments revealed that this aspartate residue is related to the apparent O2 insensitivity of the AH. Our data provide first structural insight into specialized hydrogenases that are supposed to consume atmospheric H2 under challenging conditions, i.e. at high O2 concentration and wide temperature and pH ranges.

  13. [Removal of AOX and Chroma in Biologically Treated Effluent of Chemical Dyestuff Wastewater with Nanoscale Ni/Fe].

    PubMed

    Shu, Xiao-ming; Xu, Can-can; Liu, Rui; Zhao, Yuan; Chen, Lü-jun

    2016-02-15

    Nanoscale Ni/Fe was applied to biologically treated effluent of chemical dyestuff wastewater. The removal rates of absorbable organic halogens (AOX) and chroma were investigated at different Ni loadings (0-5%), initial wastewater pH (4.1-10.0), Ni/Fe dosage (1-5 g x L(-1)) and reaction time (0.5-96 h). The results showed that the removal rates of AOX and chroma firstly increased and then decreased with the increase of the Ni loading, while continuously increased with the decrease of the initial wastewater pH and the increase of Ni/Fe dosage. The optimal condition was Ni loading of 1%, initial wastewater pH of 4.1 and Ni/Fe dosage of 3 g x L(-1), under which 29.2% of AOX and 79.6% of chroma were removed after 24 h reaction, and 50.6% of AOX and 80.7% of chroma were removed after 96 h reaction. GC-MS analysis revealed that toxicants such as chlorinated anilines, p-nitroaniline, 4-methoxy-2-nitroaniline and halogenated hydrocarbons were efficiently removed. PMID:27363157

  14. Remediation of polybrominated diphenyl ethers in soil using Ni/Fe bimetallic nanoparticles: influencing factors, kinetics and mechanism.

    PubMed

    Xie, Yingying; Fang, Zhanqiang; Cheng, Wen; Tsang, Pokeung Eric; Zhao, Dongye

    2014-07-01

    Polybrominated diphenyl ethers (PBDEs) are commonly used as additive flame retardants in all kinds of electronic products. PBDEs are now ubiquitous in the environment, with soil as a major sink, especially in e-waste recycling sites. This study investigated the degradation of decabromodiphenyl ether (BDE209) in a spiked soil using Ni/Fe bimetallic nanoparticles. The results indicated that Ni/Fe bimetallic nanoparticles are able to degrade BDE209 in soil at ambient temperature and the removal efficiency can reach 72% when an initial pH of 5.6 and at a Ni/Fe dosage of 0.03 g/g. A declining trend in degradation was noticed with decreasing Ni loading and increasing of initial BDE209 concentration. The degradation products of BDE209 were analyzed by GC-MS, which showed that the degradation of BDE209 was a process of stepwise debromination from nBr to (n-1)Br. And a possible debromination pathway was proposed. At last, the degradation process was analyzed as two-step mechanism, mass transfer and reaction. This current study shows the potential ability of Ni/Fe nanoparticles to be used for removal of PBDEs in contaminated soil. PMID:24742544

  15. Factors influencing the dechlorination of 2,4-dichlorophenol by Ni-Fe nanoparticles in the presence of humic acid.

    PubMed

    Zhang, Zhen; Cissoko, Naman; Wo, Jingjing; Xu, Xinhua

    2009-06-15

    The dechlorination of 2,4-dichlorophenol (2,4-DCP) by Ni-Fe nanoparticles in the presence of humic acid (HA) was investigated to understand the feasibility of using Ni-Fe for the in situ remediation of contaminated groundwater. 2,4-DCP was first adsorbed by Ni-Fe nanoparticles, then quickly reduced to o-chlorophenol (o-CP), p-chlorophenol (p-CP), and finally to phenol (P). However, the introduction of HA decreased the removal percentage of 2,4-DCP, as a result, the phenol production rates dropped from 86% (in the absence of HA) to 29% within 2h. Our data suggested that the dechlorination rate was dependent on a number of factors including Ni-Fe availability, Ni loading percentage over Fe, temperature, pH, and HA concentration. In particular, the removal percentage of 2,4-DCP was determined to be 100, 99, 95, 84 and 69%, for HA concentrations of 0, 5, 10, 30 and 40 mg L(-1), respectively. The kinetic calculations for the dechlorination of 2,4-DCP indicated that k values for 2,4-DCP dechlorination dropped from 0.14, 0.051, 0.039, 0.021 to 0.011 min(-1) with increasing concentrations of HA from 0, 5, 10, 30 to 40 mg L(-1).

  16. Formation of Surface Corrosion-Resistant Nanocrystalline Structures on Steel.

    PubMed

    Nykyforchyn, Hryhoriy; Kyryliv, Volodymyr; Maksymiv, Olha; Slobodyan, Zvenomyra; Tsyrulnyk, Oleksandr

    2016-12-01

    Engineering materials with nanocrystalline structure could be exploited under simultaneous action of mechanical loading and corrosion environments; therefore, their corrosion resistance is important. Surface nanocrystalline structure was generated on middle carbon steels by severe plastic deformation using the method of mechanical pulse friction treatment. This treatment additionally includes high temperature phase transformation and alloying. Using a complex of the corrosive, electrochemical and physical investigations, it was established that nanocrystalline structures can be characterized by lower or increased corrosion resistance in comparison with the reference material. It is caused by the action of two confronting factors: arising energy level and anticorrosive alloying of the surface layer.

  17. Formation of Surface Corrosion-Resistant Nanocrystalline Structures on Steel.

    PubMed

    Nykyforchyn, Hryhoriy; Kyryliv, Volodymyr; Maksymiv, Olha; Slobodyan, Zvenomyra; Tsyrulnyk, Oleksandr

    2016-12-01

    Engineering materials with nanocrystalline structure could be exploited under simultaneous action of mechanical loading and corrosion environments; therefore, their corrosion resistance is important. Surface nanocrystalline structure was generated on middle carbon steels by severe plastic deformation using the method of mechanical pulse friction treatment. This treatment additionally includes high temperature phase transformation and alloying. Using a complex of the corrosive, electrochemical and physical investigations, it was established that nanocrystalline structures can be characterized by lower or increased corrosion resistance in comparison with the reference material. It is caused by the action of two confronting factors: arising energy level and anticorrosive alloying of the surface layer. PMID:26831689

  18. Formation of Surface Corrosion-Resistant Nanocrystalline Structures on Steel

    NASA Astrophysics Data System (ADS)

    Nykyforchyn, Hryhoriy; Kyryliv, Volodymyr; Maksymiv, Olha; Slobodyan, Zvenomyra; Tsyrulnyk, Oleksandr

    2016-02-01

    Engineering materials with nanocrystalline structure could be exploited under simultaneous action of mechanical loading and corrosion environments; therefore, their corrosion resistance is important. Surface nanocrystalline structure was generated on middle carbon steels by severe plastic deformation using the method of mechanical pulse friction treatment. This treatment additionally includes high temperature phase transformation and alloying. Using a complex of the corrosive, electrochemical and physical investigations, it was established that nanocrystalline structures can be characterized by lower or increased corrosion resistance in comparison with the reference material. It is caused by the action of two confronting factors: arising energy level and anticorrosive alloying of the surface layer.

  19. Dynamics of three-dimensional helical domain wall in cylindrical NiFe nanowires

    NASA Astrophysics Data System (ADS)

    Wong, D. W.; Chandra Sekhar, M.; Gan, W. L.; Purnama, I.; Lew, W. S.

    2015-05-01

    We report on a micromagnetic study on the dynamics of current-driven helical domain wall (DW) in cylindrical NiFe nanowires. The helical DW is a three-dimensional transition region between magnetizations with clockwise and anticlockwise vortex orientations. A minimum current density is needed to overcome an intrinsic pinning to drive the helical DW, and the propagation along the nanowire is accompanied by a rotational motion. As the driving current strength is increased, the rotation ceases while the DW propagates at an increased velocity. However, a velocity barrier is experienced which results in the decrease of the DW mobility. Throughout its motion, the propagated helical DW maintains a stable profile without showing any sign of structural breakdown even at relatively high driving current.

  20. Measurements of exchange anisotropy in NiFe/NiO films with different techniques

    NASA Astrophysics Data System (ADS)

    Fermin, J. R.; Lucena, M. A.; Azevedo, A.; de Aguiar, F. M.; Rezende, S. M.

    2000-05-01

    One of the puzzles of the recent investigations on the exchange anisotropy in ferromagnetic (FM)/antiferromagnetic (AF) bilayers is the fact that different techniques yield different values for the exchange field (HE) between the layers. We report an investigation on sputtered NiFe/NiO carried out with three different techniques, namely, magneto-optical Kerr effect magnetometry (MOKE), Brillouin light scattering (BLS), and ferromagnetic resonance (FMR). In an attempt to reconcile the measurements obtained with the various techniques, we interpret the data with a model that includes the formation of a planar domain wall in the AF layer, giving rise to a torque on the FM moment represented by an effective domain wall field (HW). We find out that while the same pair of values of HE and HW provide equally good fits to the reversible FMR and BLS measurements, different pairs are necessary to fit the irreversible magnetometry data.

  1. Highly Laminated Soft Magnetic Electroplated CoNiFe Thick Films

    SciTech Connect

    Kim, J; Kim, M; Herrault, F; Park, J; Allen, MG

    2013-01-01

    The fabrication and characterization of highly laminated (similar to 40 layers), thick (similar to 40 mu m) films of magnetically soft cobalt-nickel-iron are presented. Thick film fabrication is based on automated sequential electrodeposition of alternating CoNiFe and copper layers, followed by selective copper removal. The film, comprised tens of 1 mu m thick laminations, exhibits saturation flux density of 1.8 T and coercivity of approximately 1.3 Oe. High-frequency film characterization took place in a 36-turn test inductor, which demonstrated constant inductance of 1.6 mu H up to 10 MHz, indicating suppressed eddy-current loss. Quality factor exceeding 40 at 1 MHz, surpassing the performance of similarly fabricated Permalloy (Ni80Fe20) films.

  2. Cu--Ni--Fe anode for use in aluminum producing electrolytic cell

    DOEpatents

    Bergsma, S. Craig; Brown, Craig W.; Bradford, Donald R; Barnett, Robert J.; Mezner, Michael B.

    2006-07-18

    A method of producing aluminum in an electrolytic cell containing alumina dissolved in an electrolyte, the method comprising the steps of providing a molten salt electrolyte at a temperature of less than 900.degree. C. having alumina dissolved therein in an electrolytic cell having a liner for containing the electrolyte, the liner having a bottom and walls extending upwardly from said bottom. A plurality of non-consumable Cu--Ni--Fe anodes and cathodes are disposed in a vertical direction in the electrolyte, the cathodes having a plate configuration and the anodes having a flat configuration to compliment the cathodes. The anodes contain apertures therethrough to permit flow of electrolyte through the apertures to provide alumina-enriched electrolyte between the anodes and the cathodes. Electrical current is passed through the anodes and through the electrolyte to the cathodes, depositing aluminum at the cathodes and producing gas at the anodes.

  3. Magnetization reversal of uncompensated Fe moments in exchangebiased Ni/FeF2 bilayers

    SciTech Connect

    Arenholz, Elke; Liu, Kai; Li, Zhipan; Schuller, Ivan K.

    2006-01-01

    The magnetization reversal of uncompensated Fe moments in exchange biased Ni/FeF{sub 2} bilayers was determined using soft x-ray magnetic circular and linear dichroism. The hysteresis loops resulting from the Fe moments are almost identical to those of the ferromagnetic Ni layer. However, a vertical loop shift indicates that some Fe moments are pinned in the antiferromagnetically ordered FeF{sub 2}. The pinned moments are oriented antiparallel to small cooling fields leading to negative exchange bias, but parallel to large cooling fields resulting in positive exchange bias. No indication for the formation of a parallel antiferromagnetic domain wall in the FeF{sub 2} layer upon magnetization reversal in the Ni layer was found.

  4. Structural and magnetic properties of Ni/Fe nanostructures on Ir(111)

    NASA Astrophysics Data System (ADS)

    Iaia, Davide; Kubetzka, André; von Bergmann, Kirsten; Wiesendanger, Roland

    2016-04-01

    The structural and magnetic properties of one atomic layer thin nanostructures of Ni deposited on fcc Fe monolayer stripes on Ir(111) have been studied by (spin-resolved) scanning tunneling microscopy measurements. Ni grows dominantly in fcc stacking on Ir(111), whereas it forms a dense reconstruction pattern on Fe/Ir(111), with bridge site dislocation lines separating triangularly shaped fcc and hcp regions. In the interior of the Ni nanostructures, fcc and hcp areas are of comparable size, but the fcc stacking dominates at the edges. The magnetic nanoskyrmion lattice of Fe/Ir(111) undergoes a transition to ferromagnetism where covered with a single layer of Ni. The Ni/Fe bilayer islands show an out-of-plane easy axis and can be switched by external magnetic fields of only 1.0 T-1.5 T.

  5. NiFe2O4-based cermet inert anodes for aluminum electrolysis

    NASA Astrophysics Data System (ADS)

    Li, Wangxing; Zhang, Gang; Li, Jie; Lai, Yanqing

    2009-05-01

    Recent developments in the preparation, sintering process, mechanical properties, and thermal shock resistance of cermet inert anodes for aluminum electrolysis are reviewed in this paper. To obtain the desired technologies of low-temperature activated sintering of cermet inert anodes, the effects of material composition, sintering atmosphere, sintering temperature, and sintering aids on the densifi cation and microstructure of NiFe2O4-10NiO- based ceramics and cermets were studied. To obtain the toughening and strengthening technology of the cermet, the effects of material composition including ceramic and metallic phases are discussed. The cermet inert anodes with high density and mechanical properties were prepared through adjustment of material composition and sintering technology and selection of feasible sintering aids.

  6. Rates and Routes of Electron Transfer of [NiFe]-Hydrogenase in an Enzymatic Fuel Cell.

    PubMed

    Petrenko, Alexander; Stein, Matthias

    2015-10-29

    Hydrogenase enzymes are being used in enzymatic fuel cells immobilized on a graphite or carbon electrode surface, for example. The enzyme is used for the anodic oxidation of molecular hydrogen (H2) to produce protons and electrons. The association and orientation of the enzyme at the anode electrode for a direct electron transfer is not completely resolved. The distal FeS-cluster in [NiFe]-hydrogenases contains a histidine residue which is known to play a critical role in the intermolecular electron transfer between the enzyme and the electrode surface. The [NiFe]-hydrogenase graphite electrode association was investigated using Brownian Dynamics simulations. Residues that were shown to be in proximity to the electrode surface were identified (His184, Ser196, Glu461, Glu464), and electron transfer routes connecting the distal FeS-cluster with the surface residues were investigated. Several possible pathways for electron transfer between the distal FeS-cluster and the terminal amino acid residues were probed in terms of their rates of electron transfer using DFT methods. The reorganization energies λ of the distal iron-sulfur cluster and coronene as a molecular model for graphite were calculated. The reorganization energy of the distal (His)(Cys)3 cluster was found to be not very different from that of a standard cubane clusters with a (Cys)4 coordination. Electronic coupling matrix elements and rates of electron transfer for the different pathways were calculated according to the Marcus equation. The rates for glutamate-mediated electrode binding were found to be incompatible with experimental data. A direct electron transfer from the histidine ligand of the distal FeS-cluster to the electrode yielded rates of electron transfer in excellent agreement with experiment. A second pathway, however, from the distal FeS-cluster to the Ser196 residue was found to be equally efficient and feasible. PMID:26218232

  7. Photosensitivity of the Ni-A state of [NiFe] hydrogenase from Desulfovibrio vulgaris Miyazaki F with visible light

    SciTech Connect

    Osuka, Hisao; Shomura, Yasuhito; Komori, Hirofumi; Shibata, Naoki; Nagao, Satoshi; Higuchi, Yoshiki; Hirota, Shun

    2013-01-04

    Highlights: Black-Right-Pointing-Pointer Ni-A state of [NiFe] hydrogenase showed light sensitivity. Black-Right-Pointing-Pointer New FT-IR bands were observed with light irradiation of the Ni-A state. Black-Right-Pointing-Pointer EPR g-values of the Ni-A state shifted upon light irradiation. Black-Right-Pointing-Pointer The light-induced state converted back to the Ni-A state under the dark condition. -- Abstract: [NiFe] hydrogenase catalyzes reversible oxidation of molecular hydrogen. Its active site is constructed of a hetero dinuclear Ni-Fe complex, and the oxidation state of the Ni ion changes according to the redox state of the enzyme. We found that the Ni-A state (an inactive unready, oxidized state) of [NiFe] hydrogenase from Desulfovibrio vulgaris Miyazaki F (DvMF) is light sensitive and forms a new state (Ni-AL) with irradiation of visible light. The Fourier transform infrared (FT-IR) bands at 1956, 2084 and 2094 cm{sup -1} of the Ni-A state shifted to 1971, 2086 and 2098 cm{sup -1} in the Ni-AL state. The g-values of g{sub x} = 2.30, g{sub y} = 2.23 and g{sub z} = 2.01 for the signals in the electron paramagnetic resonance (EPR) spectrum of the Ni-A state at room temperature varied for -0.009, +0.012 and +0.010, respectively, upon light irradiation. The light-induced Ni-AL state converted back immediately to the Ni-A state under dark condition at room temperature. These results show that the coordination structure of the Fe site of the Ni-A state of [NiFe] hydrogenase is perturbed significantly by light irradiation with relatively small coordination change at the Ni site.

  8. Cold-Spray Processing of a High Density Nanocrystalline Aluminum Alloy 2009 Coating Using a Mixture of As-Atomized and As-Cryomilled Powders

    NASA Astrophysics Data System (ADS)

    Zhang, Y. Y.; Wu, X. K.; Cui, H.; Zhang, J. S.

    2011-09-01

    In this work, a mixture of as-atomized and as-cryomilled powders instead of the pure as-cryomilled powder was used as feedstock to achieve high density nanocrystalline coatings by cold spraying. Cryomilled powder with nanocrystalline grains was produced by mechanical milling under liquid nitrogen and the grain size range was from 5 to 30 nm. A mixture of 30 wt.% as-atomized powder and 70 wt.% as-cryomilled powder was sprayed onto the aluminum substrates. High density coatings were attained by use of this kind of mixture, which was described as an effective method to decrease porosity in the cold-sprayed nanocrystalline coating. The functions of the as-atomized powder in the coating were discussed. The mechanical behavior of the powders and the coating were studied using nanoindentation technique.

  9. Solid state consolidation nanocrystalline copper-tungsten using cold spray

    SciTech Connect

    Hall, Aaron Christopher; Sarobol, Pylin; Argibay, Nicolas; Clark, Blythe; Diantonio, Christopher

    2015-09-01

    It is well known that nanostructured metals can exhibit significantly improved properties compared to metals with conventional grain size. Unfortunately, nanocrystalline metals typically are not thermodynamically stable and exhibit rapid grain growth at moderate temperatures. This severely limits their processing and use, making them impractical for most engineering applications. Recent work has shown that a number of thermodynamically stable nanocrystalline metal alloys exist. These alloys have been prepared as powders using severe plastic deformation (e.g. ball milling) processes. Consolidation of these powders without compromise of their nanocrystalline microstructure is a critical step to enabling their use as engineering materials. We demonstrate solid-state consolidation of ball milled copper-tantalum nanocrystalline metal powder using cold spray. Unfortunately, the nanocrystalline copper-tantalum powder that was consolidated did not contain the thermodynamically stable copper-tantalum nanostructure. Nevertheless, this does this demonstrates a pathway to preparation of bulk thermodynamically stable nanocrystalline copper-tantalum. Furthermore, it demonstrates a pathway to additive manufacturing (3D printing) of nanocrystalline copper-tantalum. Additive manufacturing of thermodynamically stable nanocrystalline metals is attractive because it enables maximum flexibility and efficiency in the use of these unique materials.

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

    PubMed Central

    Manor, Brian C.; Rauchfuss, Thomas B.

    2013-01-01

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

  11. Nanocrystalline ceramic materials

    DOEpatents

    Siegel, Richard W.; Nieman, G. William; Weertman, Julia R.

    1994-01-01

    A method for preparing a treated nanocrystalline metallic material. The method of preparation includes providing a starting nanocrystalline metallic material with a grain size less than about 35 nm, compacting the starting nanocrystalline metallic material in an inert atmosphere and annealing the compacted metallic material at a temperature less than about one-half the melting point of the metallic material.

  12. "Two-step" chronoamperometric method for studying the anaerobic inactivation of an oxygen tolerant NiFe hydrogenase.

    PubMed

    Fourmond, Vincent; Infossi, Pascale; Giudici-Orticoni, Marie-Thérèse; Bertrand, Patrick; Léger, Christophe

    2010-04-01

    Hydrogenases catalyze the oxidation and production of H(2). The fact that they could be used in biotechnological devices if they resisted inhibition by O(2) motivates the current research on their inactivation mechanism. Direct electrochemistry has been thoroughly used in this respect but often in a qualitative manner. We propose a new and precise chronoamperometric method for studying the anaerobic inactivation mechanism of hydrogenase, which we apply to the oxygen-tolerant NiFe enzyme from Aquifex aeolicus . We demonstrate that the voltammetric data cannot be used for measuring the reduction potential of the so-called NiB inactive state, even in the small scan rate limit. We show that the inactivation mechanism proposed for standard (oxygen-sensitive) NiFe hydrogenases does not apply in the case of the enzyme from A. aeolicus . In particular, the activation and inactivation reactions cannot follow the same reaction pathway.

  13. Discovery of [NiFe] hydrogenase genes in metagenomic DNA: cloning and heterologous expression in Thiocapsa roseopersicina.

    PubMed

    Maróti, Gergely; Tong, Yingkai; Yooseph, Shibu; Baden-Tillson, Holly; Smith, Hamilton O; Kovács, Kornél L; Frazier, Marvin; Venter, J Craig; Xu, Qing

    2009-09-01

    Using a metagenomics approach, we have cloned a piece of environmental DNA from the Sargasso Sea that encodes an [NiFe] hydrogenase showing 60% identity to the large subunit and 64% to the small subunit of a Thiocapsa roseopersicina O2-tolerant [NiFe] hydrogenase. The DNA sequence of the hydrogenase identified by the metagenomic approach was subsequently found to be 99% identical to the hyaA and hyaB genes of an Alteromonas macleodii hydrogenase, indicating that it belongs to the Alteromonas clade. We were able to express our new Alteromonas hydrogenase in T. roseopersicina. Expression was accomplished by coexpressing only two accessory genes, hyaD and hupH, without the need to express any of the hyp accessory genes (hypABCDEF). These results suggest that the native accessory proteins in T. roseopersicina could substitute for the Alteromonas counterparts that are absent in the host to facilitate the assembly of a functional Alteromonas hydrogenase. To further compare the complex assembly machineries of these two [NiFe] hydrogenases, we performed complementation experiments by introducing the new Alteromonas hyaD gene into the T. roseopersicina hynD mutant. Interestingly, Alteromonas endopeptidase HyaD could complement T. roseopersicina HynD to cleave endoproteolytically the C-terminal end of the T. roseopersicina HynL hydrogenase large subunit and activate the enzyme. This study refines our knowledge on the selectivity and pleiotropy of the elements of the [NiFe] hydrogenase assembly machineries. It also provides a model for functionally analyzing novel enzymes from environmental microbes in a culture-independent manner. PMID:19633107

  14. Analyses of the Large Subunit Histidine-Rich Motif Expose an Alternative Proton Transfer Pathway in [NiFe] Hydrogenases

    PubMed Central

    Szőri-Dorogházi, Emma; Maróti, Gergely; Szőri, Milán; Nyilasi, Andrea; Rákhely, Gábor; Kovács, Kornél L.

    2012-01-01

    A highly conserved histidine-rich region with unknown function was recognized in the large subunit of [NiFe] hydrogenases. The HxHxxHxxHxH sequence occurs in most membrane-bound hydrogenases, but only two of these histidines are present in the cytoplasmic ones. Site-directed mutagenesis of the His-rich region of the T. roseopersicina membrane-attached Hyn hydrogenase disclosed that the enzyme activity was significantly affected only by the replacement of the His104 residue. Computational analysis of the hydrogen bond network in the large subunits indicated that the second histidine of this motif might be a component of a proton transfer pathway including Arg487, Asp103, His104 and Glu436. Substitutions of the conserved amino acids of the presumed transfer route impaired the activity of the Hyn hydrogenase. Western hybridization was applied to demonstrate that the cellular level of the mutant hydrogenases was similar to that of the wild type. Mostly based on theoretical modeling, few proton transfer pathways have already been suggested for [NiFe] hydrogenases. Our results propose an alternative route for proton transfer between the [NiFe] active center and the surface of the protein. A novel feature of this model is that this proton pathway is located on the opposite side of the large subunit relative to the position of the small subunit. This is the first study presenting a systematic analysis of an in silico predicted proton translocation pathway in [NiFe] hydrogenases by site-directed mutagenesis. PMID:22511957

  15. Effects of Ni/Fe bimetallic nanoparticles on phytotoxicity and translocation of polybrominated diphenyl ethers in contaminated soil.

    PubMed

    Wu, Juan; Xie, Yingying; Fang, Zhanqiang; Cheng, Wen; Tsang, Pokeung Eric

    2016-11-01

    In vivo studies of the interactions of polybrominated diphenyl ethers (PBDEs) in plants have generally focused on uptake, translocation, metabolism and accumulation, but there were limited reports about the phytotoxicity and translocation of PBDEs in contaminated soil with the effects of nanoparticles. In this study, the effects of Ni/Fe bimetallic nanoparticles on translocation of polybrominated diphenyl ethers (PBDEs) in contaminated soil and its phytotoxicity to Chinese cabbage were investigated by soil culture experiments. The results showed that the plant biomass, germination rate, and shoot and root lengths of treated soil (S-5) increased by 0.0044 g, 15%, and 5 and 6 mm, respectively, compared with untreated soil (S-2B). The average Ni and Fe contents of the edible parts(stem and leaf) of the S-5 sample, which contained 0.03 g/g Ni/Fe and 10 mg/kg BDE209, were measured at 1.71 and 184 mg/kg, respectively. The superoxide dismutase, peroxidase and catalase activities in the S-5 sample decreased by 12%, 6.1% and 5.9%, respectively, while compared with the S-2B sample. In all treatments, the contents of BDE209 and the total PBDEs in sample S-5 were lowest, suggesting that the fresh Ni/Fe nanoparticles had higher toxicity than that of the aged nanoparticles. And the lower brominated PBDEs (tri-to nona-) were detected in samples, indicating uptake, debromination and/or metabolism of PBDEs existed in plants. The phytotoxicity and translocation of BDE209 in the contaminated soil decreased as a result of the effects of the Ni/Fe bimetallic nanoparticles. PMID:27501310

  16. Dihydrogen activation by sulfido-bridged dinuclear Ru/Ge complexes: insight into the [NiFe] hydrogenase unready state.

    PubMed

    Matsumoto, Tsuyoshi; Itakura, Naohisa; Nakaya, Yukiko; Tatsumi, Kazuyuki

    2011-01-21

    A S/SH bridged hetero-dinuclear Ru/Ge complex cation reacted with H(2) to afford the μ-S/μ-H complex. The reaction was considerably slower compared to that of the μ-S/μ-OH complex. Thus, the μ-S/μ-SH and μ-S/μ-OH complexes might provide models for the unready and ready states, respectively, of [NiFe] hydrogenase. PMID:21072402

  17. Degradation of aniline by heterogeneous Fenton's reaction using a Ni-Fe oxalate complex catalyst.

    PubMed

    Liu, Yucan; Zhang, Guangming; Fang, Shunyan; Chong, Shan; Zhu, Jia

    2016-11-01

    A Ni-Fe oxalate complex catalyst was synthesized and characterized by means of Brunauer-Emmet-Teller (BET) method, scanning electron microscope (SEM) and X-ray photo-electron spectroscopy (XPS). The catalyst showed good catalytic activity for aniline degradation by heterogeneous Fenton's reaction, in which the synergetic index was 9.3. The effects of reaction temperature, catalyst dosage, hydrogen peroxide concentration and initial pH were investigated. Under the optimum conditions (T = 293 K, catalyst dosage = 0.2 g/L, H2O2 concentration = 4 mmol/L and initial pH = 5.4), 100% aniline could be removed within 35 min, and approximately 88% deamination efficiency was achieved in 60 min. The aniline degradation process followed the pseudo-first-order kinetic (k = 0.177 min(-1)) with activation energy (Ea) of 49.4 kJ mol(-1). Aniline could be removed in a broad initial pH (3-8) due to the excellent pH-tolerance property of the catalyst. The detected ammonium ion indicated that deamination occurred during aniline degradation. It was proposed that deamination synchronized with aniline removal, and aniline was attacked by free radicals to generate benzoquinonimine and phenol. This system is promising for the removal of aniline from water. PMID:27498271

  18. Switching magnetic interactions in the NiFe Prussian Blue Analogue: an ab initio inspection.

    PubMed

    Krah, Tim; Amor, Nadia Ben; Robert, Vincent

    2014-05-28

    The magnetic interaction in the Ni(ii)-Fe(iii) Prussian Blue Analogue is investigated by means of Difference Dedicated Configuration Interaction (DDCI) calculations. Embedded cluster calculations are performed to extract the exchange coupling constant J with respect to an opening of the Ni-NC-Fe bridge while maintaining a rigid Fe(CN)6 unit. It is shown that such active distortion significantly modifies the magnetic interaction scheme in the material. Not only a ferromagnetic to antiferromagnetic transition is observed, but the J value is varied from +11.4 cm(-1) to -12.5 cm(-1) when the Ni-Fe cyanide bridge is opened by 20°. The enhancement of the intersite hopping electron transfer integral by a factor of 1.5 can be correlated with the observed Na(+)-ion mobility in a unified "cation-coupled electron transfer" (CCET) process. These results stress the complexity and originality of this class of compounds evidenced by the versatility of their magnetic network.

  19. Microstructure Modeling of a Ni-Fe-Based Superalloy During the Rotary Forging Process

    NASA Astrophysics Data System (ADS)

    Loyda, A.; Hernández-Muñoz, G. M.; Reyes, L. A.; Zambrano-Robledo, P.

    2016-06-01

    The microstructure evolution of Ni-Fe superalloys has a great influence on the mechanical behavior during service conditions. The rotary forging process offers an alternative to conventional bulk forming processes where the parts can be rotary forged with a fraction of the force commonly needed by conventional forging techniques. In this investigation, a numerical modeling of microstructure evolution for design and optimization of the hot forging operations has been used to manufacture a heat-resistant nickel-based superalloy. An Avrami model was implemented into finite element commercial platform DEFORM 3D to evaluate the average grain size and recrystallization during the rotary forging process. The simulations were carried out considering three initial temperatures, 980, 1000, and 1050 °C, to obtain the microstructure behavior after rotary forging. The final average grain size of one case was validated by comparing with results of previous experimental work of disk forging operation. This investigation was aimed to explore the influence of the rotary forging process on microstructure evolution in order to obtain a homogenous and refined grain size in the final component.

  20. Impact of biquadratic coupling on critical current density in Co/Cu/Ni-Fe nanopillar

    NASA Astrophysics Data System (ADS)

    Aravinthan, D.; Sabareesan, P.; Daniel, M.

    2016-05-01

    We have studied the effect of biquadratic coupling (BQC) on critical current density in the Co/Cu/Ni-Fe nanopillar by solving the magnetization switching dynamics of the free layer which is governed by Landau-Lifshitz-Gilbert-Slonczewski (LLGS) equation. The LLGS equation is analytically solved for the time independent case and value of the critical current density required to initiate the magnetization switching is calculated. Its value in the absence of BQC is 0.8576×1012 Am-2 and in the presence of BQC its value increases to 1.0914×1012 Am-2. BQC field is acting along the easy axis which opposes the free layer magnetization moving to the out of plane and hence the value of critical current density is high in the presence of BQC. We can reduce the critical current density by reducing the BQC field which can be achieved by making the nanopillar with minimal or no roughness in the pinned and free layer.

  1. Dynamic susceptibility evidence of surface spin freezing in ultrafine NiFe2O4 nanoparticles.

    PubMed

    Tackett, Ronald J; Bhuiya, Abdul W; Botez, Cristian E

    2009-11-01

    We investigated the dynamic behavior of ultrafine NiFe2O4 nanoparticles (average size D = 3.5 nm) that exhibit anomalous low temperature magnetic properties such as low saturation magnetization and high-field irreversibility in both M(H) and ZFC-FC processes. Besides the expected blocking of the superspin, observed at T1 approximately 45 K, the system undergoes a magnetic transition at T2 approximately 6 K. For the latter, frequency- and temperature-resolved dynamic susceptibility data reveal characteristics that are unambiguously related to collective spin freezing: the relative variation (per frequency decade) of the in-phase susceptibility peak temperature is approximately 0.025, critical dynamics analysis yields an exponent znu = 9.6 and a zero-field freezing temperature T(F) = 5.8 K, and, in a magnetic field, T(F)(H) is excellently described by the de Almeida-Thouless line delta T(F) = 1 - T(F)(H)/T(F) alpha H(2/3). Moreover, out-of-phase susceptibility versus temperature datasets collected at different frequencies collapse on a universal dynamic scaling curve. All these observations indicate the existence of a spin-glass-like surface layer that surrounds the superparamagnetic core and undergoes a transition to a frozen state upon cooling below 5.8 K.

  2. Degradation of aniline by heterogeneous Fenton's reaction using a Ni-Fe oxalate complex catalyst.

    PubMed

    Liu, Yucan; Zhang, Guangming; Fang, Shunyan; Chong, Shan; Zhu, Jia

    2016-11-01

    A Ni-Fe oxalate complex catalyst was synthesized and characterized by means of Brunauer-Emmet-Teller (BET) method, scanning electron microscope (SEM) and X-ray photo-electron spectroscopy (XPS). The catalyst showed good catalytic activity for aniline degradation by heterogeneous Fenton's reaction, in which the synergetic index was 9.3. The effects of reaction temperature, catalyst dosage, hydrogen peroxide concentration and initial pH were investigated. Under the optimum conditions (T = 293 K, catalyst dosage = 0.2 g/L, H2O2 concentration = 4 mmol/L and initial pH = 5.4), 100% aniline could be removed within 35 min, and approximately 88% deamination efficiency was achieved in 60 min. The aniline degradation process followed the pseudo-first-order kinetic (k = 0.177 min(-1)) with activation energy (Ea) of 49.4 kJ mol(-1). Aniline could be removed in a broad initial pH (3-8) due to the excellent pH-tolerance property of the catalyst. The detected ammonium ion indicated that deamination occurred during aniline degradation. It was proposed that deamination synchronized with aniline removal, and aniline was attacked by free radicals to generate benzoquinonimine and phenol. This system is promising for the removal of aniline from water.

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

    SciTech Connect

    Paterson, G. W. Gonçalves, F. J. T.; McFadzean, S.; Stamps, R. L.; O'Reilly, S.; Bowman, R.

    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 structural 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.

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

    PubMed

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

    2016-09-21

    In this work, a detailed quantum chemical study of the mechanism of [Ni(bdt)(dppf)] (Ni(II)L) catalyzed hydrogen formation [A. Gan, T. L. Groy, P. Tarakeshwar, S. K. S. Mazinani, J. Shearer, V. Mujica and A. K. Jones, J. Am. Chem. Soc., 2015, 137, 1109-1115] following an electro-chemical-electro-chemical (ECEC) pathway is reported. The complex exclusively catalyzes the reduction of protons to molecular hydrogen. The calculations suggest that the first one-electron reduction of the [Ni(II)L] catalyst is the rate limiting step of the catalytic cycle and hence, the buildup of detectable reaction intermediates is not expected. The catalytic activity of the [Ni(II)L] complex is facilitated by the flexibility of the ligand system, which allows the ligand framework to adapt to changes in the Ni oxidation state over the course of the reaction. Additionally, a comparison is made with the catalytic activity of [NiFe] hydrogenase. It is argued that the directionality of the reversible hydrogen formation reaction is controlled by the ligand field of the nickel ion and the possibility for side-on (η(2)) binding of H2: if the ligand framework does not allow for η(2) binding of H2, as is the case for [Ni(II)L], the catalyst irreversibly reduces protons. If the ligand field allows η(2) binding of H2, the catalyst can in principle work reversibly. The conditions for η(2) binding are discussed. PMID:27545687

  5. Three different [NiFe] hydrogenases confer metabolic flexibility in the obligate aerobe Mycobacterium smegmatis.

    PubMed

    Berney, Michael; Greening, Chris; Hards, Kiel; Collins, Desmond; Cook, Gregory M

    2014-01-01

    Mycobacterium smegmatis is an obligate aerobe that harbours three predicted [NiFe] hydrogenases, Hyd1 (MSMEG_2262–2263), Hyd2 (MSMEG_2720-2719) and Hyd3 (MSMEG_3931-3928). We show here that these three enzymes differ in their phylogeny, regulation and catalytic activity. Phylogenetic analysis revealed that Hyd1 groups with hydrogenases that oxidize H2 produced by metabolic processes, and Hyd2 is homologous to a novel group of putative high-affinity hydrogenases. Hyd1 and Hyd2 respond to carbon and oxygen limitation, and, in the case of Hyd1, hydrogen supplementation. Hydrogen consumption measurements confirmed that both enzymes can oxidize hydrogen. In contrast, the phylogenetic analysis and activity measurements of Hyd3 are consistent with the enzyme evolving hydrogen. Hyd3 is controlled by DosR, a regulator that responds to hypoxic conditions. The strict dependence of hydrogen oxidation of Hyd1 and Hyd2 on oxygen suggests that the enzymes are oxygen tolerant and linked to the respiratory chain. This unique combination of hydrogenases allows M. smegmatis to oxidize hydrogen at high (Hyd1) and potentially tropospheric (Hyd2) concentrations, as well as recycle reduced equivalents by evolving hydrogen (Hyd3). The distribution of these hydrogenases throughout numerous soil and marine species of actinomycetes suggests that oxic hydrogen metabolism provides metabolic flexibility in environments with changing nutrient fluxes.

  6. Thermal stability and degradation mechanism of NiFe/Cu giant magnetoresistance multilayer systems

    NASA Astrophysics Data System (ADS)

    Hecker, M.; Tietjen, D.; Schneider, C. M.; Cramer, N.; Malkinski, L.; Camley, R. E.; Celinski, Z.

    2002-05-01

    Ni80Fe20/Cu multilayers show large giant magnetoresistance (GMR) at low magnetic saturation fields. The GMR signal is known to degrade irreversibly at elevated temperatures. Clarification of the relevant deterioration mechanisms refines our basic understanding of the GMR effect and may help to improve the thermal stability of devices. We therefore investigated structural, transport, and magnetic properties of sputtered Ni80Fe20/Cu multilayers in the as-deposited state and after different anneals (up to 600 °C) by x-ray techniques, transport measurements, ferromagnetic resonance (FMR), and magneto-optical Kerr effect (MOKE). Multilayers with the second maximum of the antiferromagnetic (afm) coupling showed a sharp drop of the GMR at about 250 °C. The changes of the transport properties were associated with a series of structural alterations. These ranged from grain growth and defect reduction through texture sharpening and stress evolution up to the onset of interdiffusion. Interdiffusion changed the NiFe layer composition and the interface structure and finally caused layer intermixing with a loss of the former multilayer structure. Further insight into the magnetic behavior was gained from FMR and MOKE measurements, from which we determined the in-plane magnetic anisotropies, the strength of the afm coupling (bilinear and biquadratic), and the homogeneity of the layer magnetization as a function of the annealing temperature.

  7. Current induced magnetization switching in Co/Cu/Ni-Fe nanopillar with orange peel coupling

    SciTech Connect

    Aravinthan, D.; Daniel, M.; Sabareesan, P.

    2015-07-15

    The impact of orange peel coupling on spin current induced magnetization switching in a Co/Cu/Ni-Fe nanopillar device is investigated by solving the switching dynamics of magnetization of the free layer governed by the Landau-Lifshitz-Gilbert-Slonczewski (LLGS) equation. The value of the critical current required to initiate the magnetization switching is calculated analytically by solving the LLGS equation and verified the same through numerical analysis. Results of numerical simulation of the LLGS equation using Runge-Kutta fourth order procedure shows that the presence of orange peel coupling between the spacer and the ferromagnetic layers reduces the switching time of the nanopillar device from 67 ps to 48 ps for an applied current density of 4 × 10{sup 12}Am{sup −2}. Also, the presence of orange peel coupling reduces the critical current required to initiate switching, and in this case, from 1.65 × 10{sup 12}Am{sup −2} to 1.39 × 10{sup 12}Am{sup −2}.

  8. The role of the non-magnetic material in spin pumping and magnetization dynamics in NiFe and CoFeB multilayer systems

    SciTech Connect

    Ruiz-Calaforra, A. Brächer, T.; Lauer, V.; Pirro, P.; Heinz, B.; Geilen, M.; Chumak, A. V.; Conca, A.; Leven, B.; Hillebrands, B.

    2015-04-28

    We present a study of the effective magnetization M{sub eff} and the effective damping parameter α{sub eff} by means of ferromagnetic resonance spectroscopy on the ferromagnetic (FM) materials Ni{sub 81}Fe{sub 19} (NiFe) and Co{sub 40}Fe{sub 40}B{sub 20} (CoFeB) in FM/Pt, FM/NM, and FM/NM/Pt systems with the non-magnetic (NM) materials Ru, Cr, Al, and MgO. Moreover, for NiFe layer systems, the influence of interface effects is studied by way of thickness dependent measurements of M{sub eff} and α{sub eff}. Additionally, spin pumping in NiFe/NM/Pt is investigated by means of inverse spin Hall effect (ISHE) measurements. We observe a large dependence of M{sub eff} and α{sub eff} of the NiFe films on the adjacent NM layer. While Cr and Al do not induce a large change in the magnetic properties, Ru, Pt, and MgO affect M{sub eff} and α{sub eff} in different degrees. In particular, NiFe/Ru and NiFe/Ru/Pt systems show a large perpendicular surface anisotropy and a significant enhancement of the damping. In contrast, the magnetic properties of CoFeB films do not have a large influence of the NM adjacent material and only CoFeB/Pt systems present an enhancement of α{sub eff}. However, this enhancement is much more pronounced in NiFe/Pt. By the introduction of the NM spacer material, this enhancement is reduced. Furthermore, a difference in symmetry between NiFe/NM/Pt and NiFe/NM systems in the output voltage signal from the ISHE measurements reveals the presence of spin pumping into the Pt layer in all-metallic NiFe/NM/Pt and NiFe/Pt systems.

  9. Non-Volatile Ferroelectric Switching of Ferromagnetic Resonance in NiFe/PLZT Multiferroic Thin Film Heterostructures

    PubMed Central

    Hu, Zhongqiang; Wang, Xinjun; Nan, Tianxiang; Zhou, Ziyao; Ma, Beihai; Chen, Xiaoqin; Jones, John G.; Howe, Brandon M.; Brown, Gail J.; Gao, Yuan; Lin, Hwaider; Wang, Zhiguang; Guo, Rongdi; Chen, Shuiyuan; Shi, Xiaoling; Shi, Wei; Sun, Hongzhi; Budil, David; Liu, Ming; Sun, Nian X.

    2016-01-01

    Magnetoelectric effect, arising from the interfacial coupling between magnetic and electrical order parameters, has recently emerged as a robust means to electrically manipulate the magnetic properties in multiferroic heterostructures. Challenge remains as finding an energy efficient way to modify the distinct magnetic states in a reliable, reversible, and non-volatile manner. Here we report ferroelectric switching of ferromagnetic resonance in multiferroic bilayers consisting of ultrathin ferromagnetic NiFe and ferroelectric Pb0.92La0.08Zr0.52Ti0.48O3 (PLZT) films, where the magnetic anisotropy of NiFe can be electrically modified by low voltages. Ferromagnetic resonance measurements confirm that the interfacial charge-mediated magnetoelectric effect is dominant in NiFe/PLZT heterostructures. Non-volatile modification of ferromagnetic resonance field is demonstrated by applying voltage pulses. The ferroelectric switching of magnetic anisotropy exhibits extensive applications in energy-efficient electronic devices such as magnetoelectric random access memories, magnetic field sensors, and tunable radio frequency (RF)/microwave devices. PMID:27581071

  10. Magnetostriction of fcc(110) single-crystal films of Ni-Fe, Ni, and Co under rotating magnetic fields

    NASA Astrophysics Data System (ADS)

    Ohtani, Taiki; Kawai, Tetsuroh; Ohtake, Mitsuru; Futamotoa, Masaaki

    2014-07-01

    Ni-Fe, Ni, and Co(110) single-crystal films with uniaxial magnetic anisotropies are prepared on MgO(110) substrates by radio-frequency magnetron sputtering. The magnetostriction behavior under rotating magnetic fields is investigated. The Ni-Fe film shows waveforms consisting of a mixture of sinusoidal and triangular shapes under fields lower than 200 Oe. The peak of sinusoidal shape is observed when the field is applied along the easy magnetization axis, whereas that of triangular shape appears when the field is applied along the hard axis. With increasing the field from 200 to 300 Oe, the waveform changes to a usual sinusoidal shape. The waveform variation is related to the difference between the directions of uniaxial magnetic anisotropy and magnetization of magnetically unsaturated film. Waveforms consisting of sinusoidal and triangular shapes are also observed for the Ni and the Co films under low rotating fields. The threshold magnetic field where the shape changes to sinusoidal increases in the order of Ni-Fe < Ni < Co. The waveform is influenced by the symmetry and the strength of magnetic anisotropy.

  11. Non-Volatile Ferroelectric Switching of Ferromagnetic Resonance in NiFe/PLZT Multiferroic Thin Film Heterostructures

    NASA Astrophysics Data System (ADS)

    Hu, Zhongqiang; Wang, Xinjun; Nan, Tianxiang; Zhou, Ziyao; Ma, Beihai; Chen, Xiaoqin; Jones, John G.; Howe, Brandon M.; Brown, Gail J.; Gao, Yuan; Lin, Hwaider; Wang, Zhiguang; Guo, Rongdi; Chen, Shuiyuan; Shi, Xiaoling; Shi, Wei; Sun, Hongzhi; Budil, David; Liu, Ming; Sun, Nian X.

    2016-09-01

    Magnetoelectric effect, arising from the interfacial coupling between magnetic and electrical order parameters, has recently emerged as a robust means to electrically manipulate the magnetic properties in multiferroic heterostructures. Challenge remains as finding an energy efficient way to modify the distinct magnetic states in a reliable, reversible, and non-volatile manner. Here we report ferroelectric switching of ferromagnetic resonance in multiferroic bilayers consisting of ultrathin ferromagnetic NiFe and ferroelectric Pb0.92La0.08Zr0.52Ti0.48O3 (PLZT) films, where the magnetic anisotropy of NiFe can be electrically modified by low voltages. Ferromagnetic resonance measurements confirm that the interfacial charge-mediated magnetoelectric effect is dominant in NiFe/PLZT heterostructures. Non-volatile modification of ferromagnetic resonance field is demonstrated by applying voltage pulses. The ferroelectric switching of magnetic anisotropy exhibits extensive applications in energy-efficient electronic devices such as magnetoelectric random access memories, magnetic field sensors, and tunable radio frequency (RF)/microwave devices.

  12. In situ studies of surface of NiFe2O4 catalyst during complete oxidation of methane

    DOE PAGESBeta

    Zhang, Shiran; Shan, Junjun; Nie, Longhui; Nguyen, Luan; Wu, Zili; Tao, Franklin

    2015-12-21

    Here, NiFe2O4 with an inverse spinel structure exhibits high activity for a complete oxidation of methane at 400 °C–425 °C and a higher temperature. The surface of the catalyst and its adsorbates were well characterized with ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and in situ infrared spectroscopy (IR). In situ studies of the surface of NiFe2O4 using AP-XPS suggest the formation of methoxy-like and formate-like intermediates at a temperature lower than 200 °C, supported by the observed vibrational signatures in in situ IR studies. Evolutions of C1s photoemission features and the nominal atomic ratios of C/(Ni + Fe) of themore » catalyst surface suggest that the formate-like intermediate is transformed to product molecules CO2 and H2O in the temperature range of 250–300 °C. In situ studies suggest the formation of a spectator, – Olattice – CH2 – Olattice –. It strongly bonds to surface through C–O bonds and cannot be activated even at 400 °C.« less

  13. Non-Volatile Ferroelectric Switching of Ferromagnetic Resonance in NiFe/PLZT Multiferroic Thin Film Heterostructures.

    PubMed

    Hu, Zhongqiang; Wang, Xinjun; Nan, Tianxiang; Zhou, Ziyao; Ma, Beihai; Chen, Xiaoqin; Jones, John G; Howe, Brandon M; Brown, Gail J; Gao, Yuan; Lin, Hwaider; Wang, Zhiguang; Guo, Rongdi; Chen, Shuiyuan; Shi, Xiaoling; Shi, Wei; Sun, Hongzhi; Budil, David; Liu, Ming; Sun, Nian X

    2016-01-01

    Magnetoelectric effect, arising from the interfacial coupling between magnetic and electrical order parameters, has recently emerged as a robust means to electrically manipulate the magnetic properties in multiferroic heterostructures. Challenge remains as finding an energy efficient way to modify the distinct magnetic states in a reliable, reversible, and non-volatile manner. Here we report ferroelectric switching of ferromagnetic resonance in multiferroic bilayers consisting of ultrathin ferromagnetic NiFe and ferroelectric Pb0.92La0.08Zr0.52Ti0.48O3 (PLZT) films, where the magnetic anisotropy of NiFe can be electrically modified by low voltages. Ferromagnetic resonance measurements confirm that the interfacial charge-mediated magnetoelectric effect is dominant in NiFe/PLZT heterostructures. Non-volatile modification of ferromagnetic resonance field is demonstrated by applying voltage pulses. The ferroelectric switching of magnetic anisotropy exhibits extensive applications in energy-efficient electronic devices such as magnetoelectric random access memories, magnetic field sensors, and tunable radio frequency (RF)/microwave devices. PMID:27581071

  14. Influence of Ce4+ ions on the structural and magnetic properties of NiFe2O4

    NASA Astrophysics Data System (ADS)

    Shirsath, Sagar E.; Jadhav, Santosh S.; Toksha, B. G.; Patange, S. M.; Jadhav, K. M.

    2011-07-01

    The effect of Ce4+ substitution in NiFe2O4, with a chemical formula Ni1-2xCexFe2O4 (0 ≤ x ≤ 0.25), ferrite prepared by a solid-state reaction is presented in this paper. Ce4+ ions enter the NiFe2O4 lattice by replacing Ni2+ and swell the lattice. This enlarges the lattice constant, which results in a moderate distortion of the lattice. The r.m.s. strain increases from 0.411 × 10-3 to 0.471 × 10-3 with increasing Ce4+ content. SEM images revealed that Ce4+ promotes grain growth in NiFe2O4. It was also revealed that x-ray density and porosity decreases, whereas a significant increase in the bulk density is observed with the Ce4+ content. Substitution of Ce4+ for Ni2+ caused a decrease in the saturation magnetization from 41.3 to 25.12 emu/g and a decrease in the Curie temperature of the nickel ferrite from 830 to 594 K, whereas the coercivity increased from 59.48 to 458.25 Oe.

  15. Preparation and low-frequency microwave-absorbing properties of MWCNTs/Co-Ni/Fe3O4 hybrid material

    NASA Astrophysics Data System (ADS)

    Lu, Shao-Wei; Yuan, Chao-Jun; Jia, Cai-Xia; Ma, Ke-Ming; Wang, Xiao-Qiang

    2016-04-01

    MWCNTs/Co-Ni/Fe3O4 hybrid material has been successfully prepared by electroless plating and coprecipitation method, which is applied to the low-frequency microwave absorption. Their surface morphology, structure, magnetism and electromagnetic properties in the low-frequency range of 1-4GHz were characterized by field-emission scanning electron microscope (FE-SEM), X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and vector network analyzer. Results indicated that magnetic Co-Ni/Fe3O4 particles were attached on the surface of multi-walled carbon nanotubes successfully. The saturation magnetization of MWCNTs/Co-Ni/Fe3O4 hybrid materials was 68.6emu/g and the coercivity is 17.9 Oe. The electromagnetic and microwave absorbing properties analysis in the low-frequency range of 1-4GHz indicated that the hybrid material exhibited excellent magnetic loss and the maximum reflection loss could reach ‑13.57dB at 1.51GHz with 1.05GHz bandwidth below ‑5dB.

  16. Isothermal tuning of magnetic coercivity in NiFe/NiO/[Co/Pt] heterostructures with orthogonal easy axes

    NASA Astrophysics Data System (ADS)

    Baruth, Andrew

    2015-03-01

    Heterostructures of NiFe/NiO/[Co/Pt] with mutually orthogonal easy axes allow for isothermal tuning of the magnetic coercivity at room temperature with no associated shift in the hysteresis loop along the applied field axis. This is in contrast to what is typically seen in exchange biased heterostructures. The application of moderate dc magnetic fields of <3 kOe enhances the NiFe coercivity from 14.5 to 105 Oe. The application of a similarly sized dc magnetic field perpendicular to the film completely resets this enhancement back to 14.5 Oe. We propose that the in-plane magnetization of both the NiFe and [Co/Pt] adjacent layers greatly influences the pinning of the antiferromagnetic NiO interlayer (with a blocking temperature expected to be well below 50 K at this thickness). In addition, these heterostructures show unique high and low-field training effects due to alignment of [Co/Pt] stripe domains during field cycling. The dynamic, yet predictable, behavior of isothermally tuning the magnetic coercivity without any permanent structural/chemical modifications has potential uses in advanced magnetic logic/storage, as well as tuning the interfacial coupling in spintronic applications.

  17. Isothermal tuning of magnetic coercivity in NiFe/NiO/[Co/Pt] heterostructures with orthogonal easy axes

    NASA Astrophysics Data System (ADS)

    Baruth, A.

    2015-09-01

    Heterostructures of NiFe/NiO/[Co/Pt] with mutually orthogonal easy axes allow for isothermal tuning of the magnetic coercivity at room temperature with no associated shift in the hysteresis loop along the applied field axis. This is in contrast to what is typically seen in exchange biased heterostructures. The NiFe coercivity is enhanced from 14.5 to 105 Oe through the application of moderate dc magnetic fields of <3 kOe. This enhancement is completely reset with the application of a similarly sized dc magnetic field perpendicular to the film. The pinning of the antiferromagnetic NiO interlayer (i.e., blocking temperature, which is expected to be well below 50 K at this thickness in the absence of adjacent magnetic layers) is greatly enhanced and influenced by the in-plane magnetization of both the NiFe and [Co/Pt]. In addition, these heterostructures show unique high and low-field training effects due to alignment of [Co/Pt] stripe domains. This dynamic, yet predictable, behavior where the coercivity is isothermally tuned without any permanent structural/chemical modifications has potential uses in advanced magnetic logic/storage, as well as tuning the interfacial coupling in spintronic applications.

  18. [NiFe]-hydrogenase is essential for cyanobacterium Synechocystis sp. PCC 6803 aerobic growth in the dark

    PubMed Central

    De Rosa, Edith; Checchetto, Vanessa; Franchin, Cinzia; Bergantino, Elisabetta; Berto, Paola; Szabò, Ildikò; Giacometti, Giorgio M.; Arrigoni, Giorgio; Costantini, Paola

    2015-01-01

    The cyanobacterium Synechocystis sp. PCC 6803 has a bidirectional [NiFe]-hydrogenase (Hox hydrogenase) which reversibly reduces protons to H2. This enzyme is composed of a hydrogenase domain and a diaphorase moiety, which is distinctly homologous to the NADH input module of mitochondrial respiratory Complex I. Hox hydrogenase physiological function is still unclear, since it is not required for Synechocystis fitness under standard growth conditions. We analyzed the phenotype under prolonged darkness of three Synechocystis knock-out strains, lacking either Hox hydrogenase (ΔHoxE-H) or one of the proteins responsible for the assembly of its NiFe active site (ΔHypA1 and ΔHypB1). We found that Hox hydrogenase is required for Synechocystis growth under this condition, regardless of the functional status of its catalytic site, suggesting an additional role beside hydrogen metabolism. Moreover, quantitative proteomic analyses revealed that the expression levels of several subunits of the respiratory NADPH/plastoquinone oxidoreductase (NDH-1) are reduced when Synechocystis is grown in the dark. Our findings suggest that the Hox hydrogenase could contribute to electron transport regulation when both photosynthetic and respiratory pathways are down-regulated, and provide a possible explanation for the close evolutionary relationship between mitochondrial respiratory Complex I and cyanobacterial [NiFe]-hydrogenases. PMID:26215212

  19. Phase Evolution and Ni-Fe Granular Growth of Saprolitic Laterite Ore-CaO Mixtures during Reductive Roasting

    NASA Astrophysics Data System (ADS)

    Luo, Jun; Li, Guanghui; Peng, Zhiwei; Rao, Mingjun; Zhang, Yuanbo; Jiang, Tao

    2016-10-01

    The correlations between phase evolution, fusion behavior, and Ni-Fe granules growth of laterite ore-CaO mixtures during reductive roasting have been investigated. The minimum melting point of 1220°C of the CaO-MgO-Al2O3-SiO2 system with 17-36 wt.% CaO is demonstrated via phase diagram analysis, and this point is decreased in the presence of FeO. This reveals that the fusion behavior in close association with the Fe-Ni granular growth can be regulated by altering the contents of CaO and FeO. Promoting the generation of diopside (CaMgSi2O6) may reduce the operating temperature from 1300-1350°C to 1150-1200°C, which ensures sufficient melting phase content. Moreover, reducing the CO partial fraction lowers the fusion temperature but hinders the growth of Ni-Fe grains. The average size of Ni-Fe granules in the reduced mixture with 17 wt.% CaO reaches nearly 20 μm at 1200°C for 1 h in a 100 vol.% CO atmosphere.

  20. In situ studies of surface of NiFe2O4 catalyst during complete oxidation of methane

    NASA Astrophysics Data System (ADS)

    Zhang, Shiran; Shan, Junjun; Nie, Longhui; Nguyen, Luan; Wu, Zili; Tao, Franklin (Feng)

    2016-06-01

    NiFe2O4 with an inverse spinel structure exhibits high activity for a complete oxidation of methane at 400 °C-425 °C and a higher temperature. The surface of the catalyst and its adsorbates were well characterized with ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and in situ infrared spectroscopy (IR). In situ studies of the surface of NiFe2O4 using AP-XPS suggest the formation of methoxy-like and formate-like intermediates at a temperature lower than 200 °C, supported by the observed vibrational signatures in in situ IR studies. Evolutions of C1s photoemission features and the nominal atomic ratios of C/(Ni + Fe) of the catalyst surface suggest that the formate-like intermediate is transformed to product molecules CO2 and H2O in the temperature range of 250-300 °C. In situ studies suggest the formation of a spectator, - Olatticesbnd CH2sbnd Olattice -. It strongly bonds to surface through Csbnd O bonds and cannot be activated even at 400 °C.

  1. Identification, cloning and heterologous expression of active [NiFe]-hydrogenase 2 from Citrobacter sp. SG in Escherichia coli.

    PubMed

    Maier, Johannes A H; Ragozin, Sergey; Jeltsch, Albert

    2015-04-10

    Hydrogen (H2) is a potential alternative energy carrier which only produces water and heat upon combustion. Today, industrial hydrogen production mainly uses thermochemical processes based on fossil fuels or electrolysis of water. Therefore, biotechnological approaches to produce H2 from biomass are an interesting alternative. We introduce here a novel direct hydrogen measurement system using a semiconducting device specific for hydrogen detection. Using this device, a bacterium producing considerable amounts of hydrogen under aerobic cultivation was isolated and identified by 16S ribosomal DNA sequencing as Citrobacter sp. The enzyme responsible for the observed hydrogenase activity was partially purified by 3 chromatographic purification steps and could be identified by peptide mass fingerprinting to be a type 2 [NiFe]-hydrogenase. Expression of the [NiFe]-hydrogenase 2 containing operon from Citrobacter sp. SG in Escherichia coli allowed recombinant hydrogen production. The [NiFe]-hydrogenase 2 identified here may be useful for biotechnological hydrogen production. We speculate that the expression of the hydrogenase in Citrobacter may be an adaptation to growth in acidic conditions.

  2. Temperature dependence of the magnetostriction and the induced anisotropy in nanocrystalline FeCuNbSiB alloys, and their fluxgate properties

    SciTech Connect

    Nielsen, O.V.; Petersen, J.R.; Herzer, G.

    1994-03-01

    Making use of the stress induced magnetic anisotropy in some iron-rich FeCuNbSiD nanocrystalline materials the authors studied the thermal dependence of their magnetostriction which becomes zero below the Curie temperature. The choice of a suitable composition and annealing temperature results in materials with zero magnetostriction at room temperature. Due to the low magnetostriction these materials have very promising fluxgate properties which were studied as well.

  3. Nickel-zinc ferrite/permalloy (Ni0.5Zn0.5Fe2O4/Ni-Fe) soft magnetic nanocomposites fabricated by electro-infiltration

    NASA Astrophysics Data System (ADS)

    Wen, Xiao; Kelly, Stefan J.; Andrew, Jennifer S.; Arnold, David P.

    2016-05-01

    Magnetically soft NiZn ferrite (Ni0.5Zn0.5Fe2O4) nanoparticles are embedded within a permalloy (Ni-Fe) matrix via an electro-infiltration process as thin films intended for use as on-chip inductor cores in the MHz frequency regime. A layer of NiZn ferrite nanoparticles is first deposited, and then permalloy is electroplated through the voids to encapsulate the particles and form three-dimensional ferrite/alloy nanocomposites. The composites are estimated to contain 37% ferrite by volume and exhibit a relative permeability of ˜320, a saturation of ˜1.15 T, and an operational bandwidth of 93 MHz. Compared to a permalloy thin film of similar thickness, the nanocomposite exhibits 39% higher electrical resistivity and 50% higher bandwidth.

  4. High-temperature oxidation behavior and mechanism of a new type of wrought Ni-Fe-Cr-Al superalloy up to 1300 C

    SciTech Connect

    Huang, J.; Fang, H.; Fu, X.; Huang, F.; Wan, H.; Zhang, Q.; Deng, S.; Zu, J.

    2000-04-01

    The oxidation behavior of a new type of wrought Ni-Fe-Cr-Al superalloys has been investigated systematically in the temperature range of 1,100 to 1,300 C. Results are compared with those of alloy 214, Inconel 600, and GH 3030. It is shown that the oxidation resistance of the new superalloys is excellent and much better than that of the comparison alloys. Scanning electron microscopy (SEM), electron probe microanalysis (EPMA), and X-ray diffraction (XRD) experiments reveal that the excellent oxidation resistance of the new superalloy is due to the formation of a dense, stable and continuous Al{sub 2}O{sub 3} and Cr{sub 2}O{sub 3} oxide layer at high temperatures. Differential thermal analysis (DTA) shows that the formation of Cr{sub 2}O{sub 3} and Al{sub 2}O{sub 3} oxide layers on the new superalloy reaches a maximum at 1,060 and 1,356 C, respectively. The Cr{sub 2}O{sub 3} layer peels off easily, and the single dense Al{sub 2}O{sub 3} layer remains, giving good oxidation resistance at temperatures higher than 1,150 C. In addition, the new superalloy possesses high mechanical strength at high temperatures. On-site tests showed that the new superalloy has ideal oxidation resistance and can be used at high temperatures up to 1,300 C in various oxidizing and corrosion atmospheres, such as those containing SO{sub 2}, CO{sub 2} etc., for long periods.

  5. Engineering Hyperthermophilic Archaeon Pyrococcus furiosus to Overproduce Its Cytoplasmic [NiFe]-Hydrogenase*

    PubMed Central

    Chandrayan, Sanjeev K.; McTernan, Patrick M.; Hopkins, R. Christopher; Sun, Junsong; Jenney, Francis E.; Adams, Michael W. W.

    2012-01-01

    The cytoplasmic hydrogenase (SHI) of the hyperthermophilic archaeon Pyrococcus furiosus is an NADP(H)-dependent heterotetrameric enzyme that contains a nickel-iron catalytic site, flavin, and six iron-sulfur clusters. It has potential utility in a range of bioenergy systems in vitro, but a major obstacle in its use is generating sufficient amounts. We have engineered P. furiosus to overproduce SHI utilizing a recently developed genetic system. In the overexpression (OE-SHI) strain, transcription of the four-gene SHI operon was under the control of a strong constitutive promoter, and a Strep-tag II was added to the N terminus of one subunit. OE-SHI and wild-type P. furiosus strains had similar rates of growth and H2 production on maltose. Strain OE-SHI had a 20-fold higher transcription of the polycistronic hydrogenase mRNA encoding SHI, and the specific activity of the cytoplasmic hydrogenase was ∼10-fold higher when compared with the wild-type strain, although the expression levels of genes encoding processing and maturation of SHI were the same in both strains. Overexpressed SHI was purified by a single affinity chromatography step using the Strep-tag II, and it and the native form had comparable activities and physical properties. Based on protein yield per gram of cells (wet weight), the OE-SHI strain yields a 100-fold higher amount of hydrogenase when compared with the highest homologous [NiFe]-hydrogenase system previously reported (from Synechocystis). This new P. furiosus system will allow further engineering of SHI and provide hydrogenase for efficient in vitro biohydrogen production. PMID:22157005

  6. Hydrogens detected by subatomic resolution protein crystallography in a [NiFe] hydrogenase.

    PubMed

    Ogata, Hideaki; Nishikawa, Koji; Lubitz, Wolfgang

    2015-04-23

    The enzyme hydrogenase reversibly converts dihydrogen to protons and electrons at a metal catalyst. The location of the abundant hydrogens is of key importance for understanding structure and function of the protein. However, in protein X-ray crystallography the detection of hydrogen atoms is one of the major problems, since they display only weak contributions to diffraction and the quality of the single crystals is often insufficient to obtain sub-ångström resolution. Here we report the crystal structure of a standard [NiFe] hydrogenase (∼91.3 kDa molecular mass) at 0.89 Å resolution. The strictly anoxically isolated hydrogenase has been obtained in a specific spectroscopic state, the active reduced Ni-R (subform Ni-R1) state. The high resolution, proper refinement strategy and careful modelling allow the positioning of a large part of the hydrogen atoms in the structure. This has led to the direct detection of the products of the heterolytic splitting of dihydrogen into a hydride (H(-)) bridging the Ni and Fe and a proton (H(+)) attached to the sulphur of a cysteine ligand. The Ni-H(-) and Fe-H(-) bond lengths are 1.58 Å and 1.78Å, respectively. Furthermore, we can assign the Fe-CO and Fe-CN(-) ligands at the active site, and can obtain the hydrogen-bond networks and the preferred proton transfer pathway in the hydrogenase. Our results demonstrate the precise comprehensive information available from ultra-high-resolution structures of proteins as an alternative to neutron diffraction and other methods such as NMR structural analysis. PMID:25624102

  7. Magnetic properties and remanent magnetization of a mixture of Fe-Ni alloys simulated to the Yamato 74646 (LL6) chondrite

    NASA Astrophysics Data System (ADS)

    Nagai, H.; Momose, K.-I.; Funaki, M.

    Magnetic properties of mixtures of two alloys, 5 at pct Ni-Fe and 29 at pct Ni-Fe, containing varying (from 0.0 to 100 at pct) concentrations of the former, were investigated and compared to those of a Ni-Fe alloy mixture simulating the Yamato 74646 (LL6) chondrite; this mixture was prepared in accordance with the analysis data of Nagahara (1979). The original thermoremanent magnetization of alloy mixtures was acquired by heating for 2 h at 850 C and cooling to room temperature in a geomagnetic field. Remanent magnetization (RM) was measured during cooling at 77 K. It was found that the RM of the alloys simulating the Yamato chondrite was thermally stable. The intensity of RM obtained by cooling at 77 K in geomagnetic field increased by about 10 percent compared to the original one, whereas that acquired by cooling at 77 K in zero magnetic field decreased by about 25 percent.

  8. 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.

  9. One-pot fabrication of NiFe2O4 nanoparticles on α-Ni(OH)2 nanosheet for enhanced water oxidation

    NASA Astrophysics Data System (ADS)

    Chen, Hong; Yan, Junqing; Wu, Huan; Zhang, Yunxia; Liu, Shengzhong (Frank)

    2016-08-01

    Water splitting has been intensively investigated as a promising solution to resolve the future environmental and energy crises. The oxygen evolution reaction (OER) of the photo- and electric field-induced water splitting limits the development of other reactions, including hydrogen evolution reaction (HER). Fe, Ni and NiFe (hydro) oxide-based catalysts are generally acknowledged among the best candidates of OER catalysts for water splitting. Herein, we developed a one-pot simple hydrothermal process to assemble NiFe2O4 nanoparticles onto the α-Ni(OH)2 nanosheets. The first formed NiFe2O4 under high temperature and pressure environment induces and assists the α-Ni(OH)2 formation without any further additives, because the distance between the neighboring Ni atoms in the cubic NiFe2O4 is similar to that in the α-Ni(OH)2 {003} facets. We have synthesized a series of NiFe2O4/α-Ni(OH)2 compounds and find that the overpotential decreases with the increase of Ni(OH)2 content while the OER kinetics stays unchanged, suggesting that Ni(OH)2 plays a major role in overpotential while NiFe2O4 mainly affects the OER kinetics. The obtained NiFe2O4/α-Ni(OH)2 compounds is also found to be a promising co-catalyst for the photocatalytic water oxidation. In fact, it is even more active than the noble PtOx with acceptable stability for the oxygen generation.

  10. Nanocrystalline ceramic materials

    DOEpatents

    Siegel, R.W.; Nieman, G.W.; Weertman, J.R.

    1994-06-14

    A method is disclosed for preparing a treated nanocrystalline metallic material. The method of preparation includes providing a starting nanocrystalline metallic material with a grain size less than about 35 nm, compacting the starting nanocrystalline metallic material in an inert atmosphere and annealing the compacted metallic material at a temperature less than about one-half the melting point of the metallic material. 19 figs.

  11. Thermo-therapeutic applications of chitosan- and PEG-coated NiFe2O4 nanoparticles.

    PubMed

    Hoque, S Manjura; Tariq, Mehrin; Liba, S I; Salehin, F; Mahmood, Z H; Khan, M N I; Chattopadhayay, K; Islam, Rafiqul; Akhter, S

    2016-07-15

    The paper reports the thermo-therapeutic applications of chitosan- and PEG-coated nickel ferrite (NiFe2O4) nanoparticles. In this study NiFe2O4 nanoparticles were synthesized by the co-precipitation method, tuning the particle size through heat treatment in the temperature range from 200-800 °C for 3 h. XRD and TEM analysis revealed that the the ultrafine nanoparticles were of size 2-58 nm. Crystallinity of the NiFe2O4 nanoparticles in the as-dried condition with the particle size ∼2-3 nm was confirmed from the presence of a lattice fringe in the HRTEM image. VSM measurements showed that a superparamagnetic/ferromagnetic transition occurs with increasing particle size, which was further confirmed by Mössbauer spectroscopy. The nickel ferrite nanoparticles with optimum particle size of 10 nm were then coated with materials commonly used for biomedical applications, i.e. chitosan and PEG, to form homogeneous suspensions. The hydrodynamic diameter and the polydispersity index (PDI) were analyzed by dynamic light scattering at the physiological temperature of 37 °C and found to be 187 nm and 0.21 for chitosan-coated nanoparticles and 285 nm and 0.32 for PEG-coated ones. The specific loss power of rf induction heating by the set-up for hyperthermia and r 2 relaxivity by the nuclear magnetic resonance were determined. The results of induction heating measurements showed that the temperature attained by the nanoparticles of size 10 nm and concentration of about 20 mg ml(-1) was >70 °C (for chitosan) and >64 °C (for PEG). It has been demonstrated that the required temperature for hyperthermia heating could be tuned by tuning the particle size, shape and magnetization and the concentration of solution. For other potential biomedical applications of the NiFe2O4 nanoparticle solution, e.g. magnetic resonance imaging, the NMR studies yielded the T 1 and T 2 relaxivities as 0.348 and 89 mM(-1) s(-1) respectively. The fact that the T 2 relaxivity is orders of magnitude

  12. First-principles study of ferroelectricity induced by p-d hybridization in ferrimagnetic NiFe2O4

    NASA Astrophysics Data System (ADS)

    Jong, Un-Gi; Yu, Chol-Jun; Park, Yong-Su; Ri, Chong-Suk

    2016-09-01

    We investigate the ferrimagnetism and ferroelectricity of bulk NiFe2O4 with tetragonal P41 22 symmetry by means of density functional theory calculations using generalized gradient approximation + Hubbard U approach. Special attention is paid to finding the most energetically favorable configuration on magnetic ordering and further calculating the reliable spontaneous electric polarization. With the fully optimized crystalline structure of the most stable configuration, the spontaneous polarization is obtained to be 23 μC/cm2 along the z direction, which originates from the hybridization between the 3d states of the Fe3+ cation and the 2p states of oxygen induced by Jahn-Teller effect.

  13. Thermo-therapeutic applications of chitosan- and PEG-coated NiFe2O4 nanoparticles

    NASA Astrophysics Data System (ADS)

    Manjura Hoque, S.; Tariq, Mehrin; Liba, S. I.; Salehin, F.; Mahmood, Z. H.; Khan, M. N. I.; Chattopadhayay, K.; Islam, Rafiqul; Akhter, S.

    2016-07-01

    The paper reports the thermo-therapeutic applications of chitosan- and PEG-coated nickel ferrite (NiFe2O4) nanoparticles. In this study NiFe2O4 nanoparticles were synthesized by the co-precipitation method, tuning the particle size through heat treatment in the temperature range from 200-800 °C for 3 h. XRD and TEM analysis revealed that the the ultrafine nanoparticles were of size 2-58 nm. Crystallinity of the NiFe2O4 nanoparticles in the as-dried condition with the particle size ˜2-3 nm was confirmed from the presence of a lattice fringe in the HRTEM image. VSM measurements showed that a superparamagnetic/ferromagnetic transition occurs with increasing particle size, which was further confirmed by Mössbauer spectroscopy. The nickel ferrite nanoparticles with optimum particle size of 10 nm were then coated with materials commonly used for biomedical applications, i.e. chitosan and PEG, to form homogeneous suspensions. The hydrodynamic diameter and the polydispersity index (PDI) were analyzed by dynamic light scattering at the physiological temperature of 37 °C and found to be 187 nm and 0.21 for chitosan-coated nanoparticles and 285 nm and 0.32 for PEG-coated ones. The specific loss power of rf induction heating by the set-up for hyperthermia and r 2 relaxivity by the nuclear magnetic resonance were determined. The results of induction heating measurements showed that the temperature attained by the nanoparticles of size 10 nm and concentration of about 20 mg ml-1 was >70 °C (for chitosan) and >64 °C (for PEG). It has been demonstrated that the required temperature for hyperthermia heating could be tuned by tuning the particle size, shape and magnetization and the concentration of solution. For other potential biomedical applications of the NiFe2O4 nanoparticle solution, e.g. magnetic resonance imaging, the NMR studies yielded the T 1 and T 2 relaxivities as 0.348 and 89 mM-1 s-1 respectively. The fact that the T 2 relaxivity is orders of magnitude higher

  14. Thermo-therapeutic applications of chitosan- and PEG-coated NiFe2O4 nanoparticles

    NASA Astrophysics Data System (ADS)

    Manjura Hoque, S.; Tariq, Mehrin; Liba, S. I.; Salehin, F.; Mahmood, Z. H.; Khan, M. N. I.; Chattopadhayay, K.; Islam, Rafiqul; Akhter, S.

    2016-07-01

    The paper reports the thermo-therapeutic applications of chitosan- and PEG-coated nickel ferrite (NiFe2O4) nanoparticles. In this study NiFe2O4 nanoparticles were synthesized by the co-precipitation method, tuning the particle size through heat treatment in the temperature range from 200–800 °C for 3 h. XRD and TEM analysis revealed that the the ultrafine nanoparticles were of size 2–58 nm. Crystallinity of the NiFe2O4 nanoparticles in the as-dried condition with the particle size ∼2–3 nm was confirmed from the presence of a lattice fringe in the HRTEM image. VSM measurements showed that a superparamagnetic/ferromagnetic transition occurs with increasing particle size, which was further confirmed by Mössbauer spectroscopy. The nickel ferrite nanoparticles with optimum particle size of 10 nm were then coated with materials commonly used for biomedical applications, i.e. chitosan and PEG, to form homogeneous suspensions. The hydrodynamic diameter and the polydispersity index (PDI) were analyzed by dynamic light scattering at the physiological temperature of 37 °C and found to be 187 nm and 0.21 for chitosan-coated nanoparticles and 285 nm and 0.32 for PEG-coated ones. The specific loss power of rf induction heating by the set-up for hyperthermia and r 2 relaxivity by the nuclear magnetic resonance were determined. The results of induction heating measurements showed that the temperature attained by the nanoparticles of size 10 nm and concentration of about 20 mg ml‑1 was >70 °C (for chitosan) and >64 °C (for PEG). It has been demonstrated that the required temperature for hyperthermia heating could be tuned by tuning the particle size, shape and magnetization and the concentration of solution. For other potential biomedical applications of the NiFe2O4 nanoparticle solution, e.g. magnetic resonance imaging, the NMR studies yielded the T 1 and T 2 relaxivities as 0.348 and 89 mM‑1 s‑1 respectively. The fact that the T 2 relaxivity is orders of

  15. In-situ synthesis of magnetic (NiFe 2O 4/CuO/FeO) nanocomposites

    NASA Astrophysics Data System (ADS)

    Srivastava, Manish; Ojha, Animesh K.; Chaubey, S.; Singh, Jay

    2010-11-01

    In-situ synthesis of magnetic nanocomposites with (NiFe 2O 4/CuO/FeO) crystal phases has been done using a sol-gel method by taking a non-stoichiometric composition of the precursors. The average particle size of the nanocomposites was calculated using X-ray diffraction (XRD) and high resolution tunneling electron microscope (HR-TEM) and it turns out to be ˜20 nm. The vibrating sample magnetometer (VSM) measurements demonstrate the ferromagnetic nature of the nanocomposites. The synthesized nanocomposite was used to prepare magnetic fluid using tetramethylammonium hydroxide as a surfactant and its stability in the solution was also discussed.

  16. Unusual formation of a [NiSFe(2)(CO)(6)] cluster: a structural model for the inactive form of [NiFe] hydrogenase.

    PubMed

    Perra, Alessandro; Wang, Qiang; Blake, Alexander J; Davies, E Stephen; McMaster, Jonathan; Wilson, Claire; Schröder, Martin

    2009-02-14

    The synthesis and characterisation of the trinuclear Ni-Fe complex [Ni(L(2))SFe(2)(CO)(6)] (1) formed from the reaction of [Ni(L(1))] with Fe(3)(CO)(12) is described. The single-crystal X-ray structure of 1 shows Ni(ii) bound to three thioether R(2)-S donors and bridged by a sulfide (S(2-)) group to two Fe(CO)(3) units. undergoes a reversible one-electron reduction process at E(1/2) = -1.62 V vs. Fc(+)/Fc to generate 1 (-), which has been characterised by UV-vis and IR spectroelectrochemistry and by EPR spectroscopy. DFT calculations on 1and 1 (-) reveal electronic structures that are delocalised across the NiFe(2) core. The SOMO in 1 (-) possesses Ni-Fe and Fe-Fe anti-bonding character and lies approximately in the plane defined by the equilateral triangle of Ni and Fe atoms. It possesses d-orbital contributions of 18.5, 15.0 and 19.8% for the Ni(1), Fe(1) and Fe(2) atoms, respectively. The Ni-S(sulfide) bond length in 1 [2.1654(7) A] is identical to that for the bridging sulfide found in the oxidised inactive form of the [NiFe] hydrogenase from D. vulgaris (2.16 A). Thus, 1 provides a useful comparison for biological [NiFe] centres bridged by sulfide donors. PMID:19173074

  17. Investigation of dielectric and electrical behaviour of nanocrystalline Zn1-xMnxO (x=0 to 0.10) semiconductors synthesized by mechanical alloying

    NASA Astrophysics Data System (ADS)

    Choudhury, S.; Sain, S.; Mandal, M. K.; Pradhan, S. K.; Meikap, A. K.

    2016-07-01

    The results on the measurement of electric and dielectric behaviour and capacitance-voltage characteristics of Zn1-xMnxO (x=0 to 0.10) nanocrystalline semiconductors are reported. Direct current conductivity increases with the increase Mn concentration and its thermal behavior can be explained by adiabatic polaronic hopping model. The alternating current conductivity obeys a power law of temperature and frequency. The temperature exponent p strongly depends on Mn concentration. The temperature dependence of frequency exponent s suggests that the overlapping large polaron conduction model is the appropriate conduction mechanism for the investigated samples. The interfacial boundaries and grain contribution to the dielectric properties can be identified by the analysis of complex impedance. Relaxation behaviour of the samples can be explained from the analysis of the electric modulus. Formation of Schottky diode can be described from capacitance-voltage characteristic of the samples and different diode parameters can be extracted from it.

  18. The importance of holes in aluminium tris-8-hydroxyquinoline (Alq{sub 3}) devices with Fe and NiFe contacts

    SciTech Connect

    Zhang, Hongtao; Desai, P.; Kreouzis, T.; Zhan, Y. Q.; Drew, A. J.; Gillin, W. P.

    2014-01-06

    To study the dominant charge carrier polarity in aluminium tris-8-hydroxyquinoline (Alq{sub 3}) based spin valves, single Alq{sub 3} layer devices with NiFe, ITO, Fe, and aluminium electrodes were fabricated and characterised by Time of Flight (ToF) and Dark Injection (DI) techniques, yielding a lower hole mobility compared to electron mobility. We compare the mobility measured by DI for the dominant carrier injected from NiFe and Fe electrodes into Alq{sub 3}, to that of holes measured by ToF. This comparison leads us to conclude that the dominant charge carriers in Alq{sub 3} based spin valves with NiFe or Fe electrodes are holes.

  19. Synthesis of SiO2 coated NiFe2O4 nanoparticles and the effect of SiO2 shell thickness on the magnetic properties

    NASA Astrophysics Data System (ADS)

    Coşkun, M.; Korkmaz, M.; Fırat, T.; Jaffari, G. H.; Shah, S. I.

    2010-05-01

    In this work, the results of synthesis of core-shell NiFe2O4 nanoparticles and influence of silica coating on the magnetic properties of nanoparticles are presented. Spherical NiFe2O4 nanoparticles were prepared via a normal micelles process. NiFe2O4 nanoparticles homogeneously coated with SiO2 of various shell thickness were synthesized by reverse microemulsion. The interparticle spacing was varied by changing the amount of added tetraethylorthosilicate. The microstructures and morphologies of these nanoparticles were studied by x-ray diffraction and transmission electron microscopy techniques. The magnetic parameters such as saturation magnetizations, blocking temperatures, and magnetic anisotropies have been calculated from dc magnetization and ac susceptibility measurements.

  20. A superlattice of alternately stacked Ni-Fe hydroxide nanosheets and graphene for efficient splitting of water.

    PubMed

    Ma, Wei; Ma, Renzhi; Wang, Chengxiang; Liang, Jianbo; Liu, Xiaohe; Zhou, Kechao; Sasaki, Takayoshi

    2015-02-24

    Cost-effective electrocatalysts based on nonprecious metals for efficient water splitting are crucial for various technological applications represented by fuel cell. Here, 3d transition metal layered double hydroxides (LDHs) with varied contents of Ni and Fe were successfully synthesized through a homogeneous precipitation. The exfoliated Ni-Fe LDH nanosheets were heteroassembled with graphene oxide (GO) as well as reduced graphene oxide (rGO) into superlattice-like hybrids, in which two kinds of oppositely charged nanosheets are stacked face-to-face in alternating sequence. Heterostructured composites of Ni2/3Fe1/3 LDH nanosheets and GO (Ni2/3Fe1/3-GO) exhibited an excellent oxygen evolution reaction (OER) efficiency with a small overpotential of about 0.23 V and Tafel slope of 42 mV/decade. The activity was further improved via the combination of Ni2/3Fe1/3 LDH nanosheets with more conductive rGO (Ni2/3Fe1/3-rGO) to achieve an overpotential as low as 0.21 V and Tafel plot of 40 mV/decade. The catalytic activity was enhanced with an increased Fe content in the bimetallic Ni-Fe system. Moreover, the composite catalysts were found to be effective for hydrogen evolution reaction. An electrolyzer cell powered by a single AA battery of 1.5 V was demonstrated by using the bifunctional catalysts.

  1. Strain mediated magnetoelectric coupling in a NiFe2O4-BaTiO3 multiferroic composite

    NASA Astrophysics Data System (ADS)

    Gorige, Venkataiah; Kati, Raju; Yoon, D. H.; Kumar, P. S. Anil

    2016-10-01

    In this paper we demonstrate significant magnetoelectric coupling in ferrimagnetic, NiFe2O4, and ferroelectric, BaTiO3, multiferroic composite bulk materials by measuring temperature dependent magnetization. X-ray diffraction, scanning electron microscopy and high resolution transmission electron microscopy data show that the two phases coexist with a highly crystalline and sharp interface without any detectable impurities, which enables significant magnetoelectric (ME) coupling. The temperature dependent magnetization data of the composite clearly show the jumps in magnetization curves at the structural phase transitions of BaTiO3, thereby indicating their origin in ME coupling. The change in coercivity of composite sample in different ferroelectric phases of BaTiO3 has been observed compared to the NiFe2O4 sample. The different lattice strains corresponding to different ferroelectric phases of BaTiO3 could be the driving force for modulating the magnetization and coercivity of the composite material. This is clear evidence of strain mediated ME coupling in ferrimagnetic and ferroelectric composite materials.

  2. The Ni, Fe and CO contents of metal phases in the Allende, Holbrook and Nuevo Mercurio chondrites

    NASA Astrophysics Data System (ADS)

    Miura, Y.; Smith, D. G. W.; Launspach, S.

    1983-12-01

    The Ni, Fe and Co contents of metal phases in the Allende, Holbrook and Nuevo Mercurio chondrites have been obtained using an automated electron microprobe fitted with both wavelength and energy dispersive spectrometers. Co contents of kamacite in these chondrites are inconsistent with those reported previously, but the general tendency of Co to increase in the kamacite in chondrites from H, L to LL groups, is supported by the study. Although the variation patterns of Ni-Co observed so far for L4, H5 and CV3 chondrites are simple, six L6 chondrites, including those reported previously, show significant difference in Co contents and the concentration and abundance charcateristics of Ni-Fe-Co patterns of the metal phases. The great similarity of composition of each region of these patterns obtained from two samples of Holbrook and two samples of Allende which came from different collections, indicate that the variation patterns of Ni-Co in the metal phases provide a means of characterizing or 'fingerprinting', as do the great differences in the variation patterns of Fe-Ni-Co which occur from one chondrite to another or even within the same group and petrologic type.

  3. Flexible in-plane microsupercapacitors with electrospun NiFe2O4 nanofibers for portable sensing applications.

    PubMed

    Li, La; Lou, Zheng; Han, Wei; Shen, Guozhen

    2016-08-11

    The development of wearable electronic devices in recent decades has brought new opportunities in the exploration of micro-supercapacitors as energy storage units. In this work, we report the fabrication of flexible NiFe2O4 nanofiber based in-plane micro-supercapacitors (MSCs), which can serve as energy storage receptors to drive a portable graphene pressure sensor. The obtained NiFe2O4 nanofiber electrodes exhibited a specific capacitance of 2.23 F cm(-3) at the scan rate of 100 mV s(-1), and excellent rate capability and robust cycling stability with a capacitance retention of 93.6% after 10 000 charge/discharge cycles. Moreover, the in-plane MSCs have superior flexibility and outstanding stability even after repetition of charge/discharge cycles during the convex and concave bending states. The MSCs offered a high energy density of 0.197 mWh cm(-3) and power density up to 2.07 W cm(-3). We also coupled the MSCs with a graphene pressure sensor as a micro-integrated system to implement it's pressure response function and used MATLAB to simulate this system behavior as well. The performance of the designed systems exhibited a stable pressure response, and the simulated results coincide well with the experimental data, demonstrating its feasibility in wearable electronic devices. PMID:27466001

  4. Cu2O Photocathode for Low Bias Photoelectrochemical Water Splitting Enabled by NiFe-Layered Double Hydroxide Co-Catalyst

    NASA Astrophysics Data System (ADS)

    Qi, Huan; Wolfe, Jonathan; Fichou, Denis; Chen, Zhong

    2016-08-01

    Layered double hydroxides (LDHs) are bimetallic hydroxides that currently attract considerable attention as co-catalysts in photoelectrochemical (PEC) systems in view of water splitting under solar light. A wide spectrum of LDHs can be easily prepared on demand by tuning their chemical composition and structural morphology. We describe here the electrochemical growth of NiFe-LDH overlayers on Cu2O electrodes and study their PEC behavior. By using the modified Cu2O/NiFe-LDH electrodes we observe a remarkable seven-fold increase of the photocurrent intensity under an applied voltage as low as ‑0.2 V vs Ag/AgCl. The origin of such a pronounced effect is the improved electron transfer towards the electrolyte brought by the NiFe-LDH overlayer due to an appropriate energy level alignment. Long-term photostability tests reveal that Cu2O/NiFe-LDH photocathodes show no photocurrent loss after 40 hours of operation under light at ‑0.2 V vs Ag/AgCl low bias condition. These improved performances make Cu2O/NiFe-LDH a suitable photocathode material for low voltage H2 production. Indeed, after 8 hours of H2 production under ‑0.2 V vs Ag/AgCl the PEC cell delivers a 78% faradaic efficiency. This unprecedented use of Cu2O/NiFe-LDH as an efficient photocathode opens new perspectives in view of low biasd or self-biased PEC water splitting under sunlight illumination.

  5. Cu2O Photocathode for Low Bias Photoelectrochemical Water Splitting Enabled by NiFe-Layered Double Hydroxide Co-Catalyst

    PubMed Central

    Qi, Huan; Wolfe, Jonathan; Fichou, Denis; Chen, Zhong

    2016-01-01

    Layered double hydroxides (LDHs) are bimetallic hydroxides that currently attract considerable attention as co-catalysts in photoelectrochemical (PEC) systems in view of water splitting under solar light. A wide spectrum of LDHs can be easily prepared on demand by tuning their chemical composition and structural morphology. We describe here the electrochemical growth of NiFe-LDH overlayers on Cu2O electrodes and study their PEC behavior. By using the modified Cu2O/NiFe-LDH electrodes we observe a remarkable seven-fold increase of the photocurrent intensity under an applied voltage as low as −0.2 V vs Ag/AgCl. The origin of such a pronounced effect is the improved electron transfer towards the electrolyte brought by the NiFe-LDH overlayer due to an appropriate energy level alignment. Long-term photostability tests reveal that Cu2O/NiFe-LDH photocathodes show no photocurrent loss after 40 hours of operation under light at −0.2 V vs Ag/AgCl low bias condition. These improved performances make Cu2O/NiFe-LDH a suitable photocathode material for low voltage H2 production. Indeed, after 8 hours of H2 production under −0.2 V vs Ag/AgCl the PEC cell delivers a 78% faradaic efficiency. This unprecedented use of Cu2O/NiFe-LDH as an efficient photocathode opens new perspectives in view of low biasd or self-biased PEC water splitting under sunlight illumination. PMID:27487918

  6. Cu2O Photocathode for Low Bias Photoelectrochemical Water Splitting Enabled by NiFe-Layered Double Hydroxide Co-Catalyst.

    PubMed

    Qi, Huan; Wolfe, Jonathan; Fichou, Denis; Chen, Zhong

    2016-01-01

    Layered double hydroxides (LDHs) are bimetallic hydroxides that currently attract considerable attention as co-catalysts in photoelectrochemical (PEC) systems in view of water splitting under solar light. A wide spectrum of LDHs can be easily prepared on demand by tuning their chemical composition and structural morphology. We describe here the electrochemical growth of NiFe-LDH overlayers on Cu2O electrodes and study their PEC behavior. By using the modified Cu2O/NiFe-LDH electrodes we observe a remarkable seven-fold increase of the photocurrent intensity under an applied voltage as low as -0.2 V vs Ag/AgCl. The origin of such a pronounced effect is the improved electron transfer towards the electrolyte brought by the NiFe-LDH overlayer due to an appropriate energy level alignment. Long-term photostability tests reveal that Cu2O/NiFe-LDH photocathodes show no photocurrent loss after 40 hours of operation under light at -0.2 V vs Ag/AgCl low bias condition. These improved performances make Cu2O/NiFe-LDH a suitable photocathode material for low voltage H2 production. Indeed, after 8 hours of H2 production under -0.2 V vs Ag/AgCl the PEC cell delivers a 78% faradaic efficiency. This unprecedented use of Cu2O/NiFe-LDH as an efficient photocathode opens new perspectives in view of low biasd or self-biased PEC water splitting under sunlight illumination. PMID:27487918

  7. Selective aluminum dissolution as a means to observe the microstructure of nanocrystalline intermetallic phases from Al-Fe-Cr-Ti-Ce rapidly solidified alloy.

    PubMed

    Michalcová, Alena; Vojtěch, Dalibor; Novák, Pavel

    2013-02-01

    Rapidly solidified aluminum alloys are promising materials with very fine microstructure. The microscopy observation of these materials is complicated due to overlay of fcc-Al matrix and different intermetallic phases. A possible way to solve this problem is to dissolve the Al matrix. By this process powder formed by single intermetallic phase particles is obtained. In this paper a new aqueous based dissolving agent for Al-based alloy is presented. The influence of oxidation agent (FeCl(3)) concentration on quality of extraction process was studied. PMID:23177792

  8. Characterization of NiPt, FePt, and NiFePt nanoparticles

    NASA Astrophysics Data System (ADS)

    Sutherland, Greg; Wood, Darren; Jackson, Amy; Warren, Andrew; Coffey, Kevin; Vanfleet, Richard

    2012-10-01

    Many metal alloys can form in chemically ordered structures, often resulting in significant changes in properties. The ordered structures are preferred at low temperatures and will go through an order-disorder phase transition at a critical temperature. The formation and stability of these ordered structures in alloy nanoparticles is not well understood but may give insight into the role size plays in phase transitions. To this end we are studying FePt, NiPt, and FeNiPt alloy nanoparticles. We will focus this presentation on the characterization of these nanoparticles in a Transmission Electron Microscope (TEM) for composition, size, and structure. These nanoparticles are made by co-sputtering the constituents and annealing at different temperatures in various gas mixtures. The nanoparticle samples are prepared for TEM viewing by wedge polishing. We find FePt to be ``well behaved'' meaning this alloy forms particles, retains the as deposited composition, and chemically orders as expected. However, the order-disorder temperature is too high for the desired further studies. NiPt, which has a lower order-disorder temperature, is not ``well behaved'' in that the nanoparticle compositions are not good matches to the as deposited conditions and no chemical ordering has been achieved even under conditions that should be sufficient based on bulk processing. We will discuss these results and possible implications.

  9. A soil actinobacterium scavenges atmospheric H2 using two membrane-associated, oxygen-dependent [NiFe] hydrogenases.

    PubMed

    Greening, Chris; Berney, Michael; Hards, Kiel; Cook, Gregory M; Conrad, Ralf

    2014-03-18

    In the Earth's lower atmosphere, H2 is maintained at trace concentrations (0.53 ppmv/0.40 nM) and rapidly turned over (lifetime ≤ 2.1 y(-1)). It is thought that soil microbes, likely actinomycetes, serve as the main global sink for tropospheric H2. However, no study has ever unambiguously proven that a hydrogenase can oxidize this trace gas. In this work, we demonstrate, by using genetic dissection and sensitive GC measurements, that the soil actinomycete Mycobacterium smegmatis mc(2)155 constitutively oxidizes subtropospheric concentrations of H2. We show that two membrane-associated, oxygen-dependent [NiFe] hydrogenases mediate this process. Hydrogenase-1 (Hyd1) (MSMEG_2262-2263) is well-adapted to rapidly oxidize H2 at a range of concentrations [Vmax(app) = 12 nmol⋅g⋅dw(-1)⋅min(-1); Km(app) = 180 nM; threshold = 130 pM in the Δhyd23 (Hyd1 only) strain], whereas Hyd2 (MSMEG_2719-2720) catalyzes a slower-acting, higher-affinity process [Vmax(app) = 2.5 nmol⋅g⋅dw(-1)⋅min(-1); Km(app) = 50 nM; threshold = 50 pM in the Δhyd13 (Hyd2 only) strain]. These observations strongly support previous studies that have linked group 5 [NiFe] hydrogenases (e.g., Hyd2) to the oxidation of tropospheric H2 in soil ecosystems. We further reveal that group 2a [NiFe] hydrogenases (e.g., Hyd1) can contribute to this process. Hydrogenase expression and activity increases in carbon-limited cells, suggesting that scavenging of trace H2 helps to sustain dormancy. Distinct physiological roles for Hyd1 and Hyd2 during the adaptation to this condition are proposed. Soil organisms harboring high-affinity hydrogenases may be especially competitive, given that they harness a highly dependable fuel source in otherwise unstable environments.

  10. A soil actinobacterium scavenges atmospheric H2 using two membrane-associated, oxygen-dependent [NiFe] hydrogenases

    PubMed Central

    Greening, Chris; Berney, Michael; Hards, Kiel; Cook, Gregory M.; Conrad, Ralf

    2014-01-01

    In the Earth’s lower atmosphere, H2 is maintained at trace concentrations (0.53 ppmv/0.40 nM) and rapidly turned over (lifetime ≤ 2.1 y−1). It is thought that soil microbes, likely actinomycetes, serve as the main global sink for tropospheric H2. However, no study has ever unambiguously proven that a hydrogenase can oxidize this trace gas. In this work, we demonstrate, by using genetic dissection and sensitive GC measurements, that the soil actinomycete Mycobacterium smegmatis mc2155 constitutively oxidizes subtropospheric concentrations of H2. We show that two membrane-associated, oxygen-dependent [NiFe] hydrogenases mediate this process. Hydrogenase-1 (Hyd1) (MSMEG_2262-2263) is well-adapted to rapidly oxidize H2 at a range of concentrations [Vmax(app) = 12 nmol⋅g⋅dw−1⋅min−1; Km(app) = 180 nM; threshold = 130 pM in the Δhyd23 (Hyd1 only) strain], whereas Hyd2 (MSMEG_2719-2720) catalyzes a slower-acting, higher-affinity process [Vmax(app) = 2.5 nmol⋅g⋅dw−1⋅min−1; Km(app) = 50 nM; threshold = 50 pM in the Δhyd13 (Hyd2 only) strain]. These observations strongly support previous studies that have linked group 5 [NiFe] hydrogenases (e.g., Hyd2) to the oxidation of tropospheric H2 in soil ecosystems. We further reveal that group 2a [NiFe] hydrogenases (e.g., Hyd1) can contribute to this process. Hydrogenase expression and activity increases in carbon-limited cells, suggesting that scavenging of trace H2 helps to sustain dormancy. Distinct physiological roles for Hyd1 and Hyd2 during the adaptation to this condition are proposed. Soil organisms harboring high-affinity hydrogenases may be especially competitive, given that they harness a highly dependable fuel source in otherwise unstable environments. PMID:24591586

  11. Features of formation of nanocrystalline state in internal- oxidized V-Cr-Zr-W and V-Mo-Zr system alloys during deformation by torsion under pressure

    NASA Astrophysics Data System (ADS)

    Smirnov, I. V.; Ditenberg, I. A.; Grinayev, K. V.; Radishevsky, V. L.

    2016-02-01

    The results of investigation of features of nanostructural state formed during deformation by torsion under pressure in high-strength vanadium V-Cr-Zr-W and V-Mo-Zr systems alloys are presented. It was found that after deformation at number of revolutions N = 1, samples are characterized by high anisotropy of defect and grain structure. Inside grains, limited by high-angle boundaries, the formation of two-level structure states was revealed: fragmentation of the above grains on nanofragments from 5 to 20 nm in size with a dipole nature of low-angle misorientations and high (hundreds of degrees per micron) elastic curvature of crystal lattice. Formation of the above structural states leads to a 3-fold increase in microhardness values. Further increase in deformation degree leads to fracture of samples of vanadium alloy V-Mo-Zr with a high volumetric content of fine-disperse oxide phase. At the same time V-Cr-Zr-W-system alloy with a lower concentration of Zr and, as a result, a lower volume fraction of fine particles remains ductile.

  12. Identification of Optimum Magnetic Behavior of NanoCrystalline CmFeAl Type Heusler Alloy Powders Using Response Surface Methodology

    NASA Astrophysics Data System (ADS)

    Srivastava, Y.; Srivastava, S.; Boriwal, L.

    2016-09-01

    Mechanical alloying is a novelistic solid state process that has received considerable attention due to many advantages over other conventional processes. In the present work, Co2FeAl healer alloy powder, prepared successfully from premix basic powders of Cobalt (Co), Iron (Fe) and Aluminum (Al) in stoichiometric of 60Co-26Fe-14Al (weight %) by novelistic mechano-chemical route. Magnetic properties of mechanically alloyed powders were characterized by vibrating sample magnetometer (VSM). 2 factor 5 level design matrix was applied to experiment process. Experimental results were used for response surface methodology. Interaction between the input process parameters and the response has been established with the help of regression analysis. Further analysis of variance technique was applied to check the adequacy of developed model and significance of process parameters. Test case study was performed with those parameters, which was not selected for main experimentation but range was same. Response surface methodology, the process parameters must be optimized to obtain improved magnetic properties. Further optimum process parameters were identified using numerical and graphical optimization techniques.

  13. Compressibility of Nanocrystalline Forsterite

    SciTech Connect

    Couvy, H.; Chen, J; Drozd, V

    2010-01-01

    We established an equation of state for nanocrystalline forsterite using multi-anvil press and diamond anvil cell. Comparative high-pressure and high-temperature experiments have been performed up to 9.6 GPa and 1,300 C. We found that nanocrystalline forsterite is more compressible than macro-powder forsterite. The bulk modulus of nanocrystalline forsterite is equal to 123.3 ({+-}3.4) GPa whereas the bulk modulus of macro-powder forsterite is equal to 129.6 ({+-}3.2) GPa. This difference is attributed to a weakening of the elastic properties of grain boundary and triple junction and their significant contribution in nanocrystalline sample compare to the bulk counterpart. The bulk modulus at zero pressure of forsterite grain boundary was determined to be 83.5 GPa.

  14. Creating bulk nanocrystalline metal.

    SciTech Connect

    Fredenburg, D. Anthony; Saldana, Christopher J.; Gill, David D.; Hall, Aaron Christopher; Roemer, Timothy John; Vogler, Tracy John; Yang, Pin

    2008-10-01

    Nanocrystalline and nanostructured materials offer unique microstructure-dependent properties that are superior to coarse-grained materials. These materials have been shown to have very high hardness, strength, and wear resistance. However, most current methods of producing nanostructured materials in weapons-relevant materials create powdered metal that must be consolidated into bulk form to be useful. Conventional consolidation methods are not appropriate due to the need to maintain the nanocrystalline structure. This research investigated new ways of creating nanocrystalline material, new methods of consolidating nanocrystalline material, and an analysis of these different methods of creation and consolidation to evaluate their applicability to mesoscale weapons applications where part features are often under 100 {micro}m wide and the material's microstructure must be very small to give homogeneous properties across the feature.

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

    PubMed

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

    2016-04-25

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

  16. Facile hybridization of Ni@Fe2O3 superparticles with functionalized reduced graphene oxide and its application as anode material in lithium-ion batteries.

    PubMed

    Backert, Gregor; Oschmann, Bernd; Tahir, Muhammad Nawaz; Mueller, Franziska; Lieberwirth, Ingo; Balke, Benjamin; Tremel, Wolfgang; Passerini, Stefano; Zentel, Rudolf

    2016-09-15

    In our present work we developed a novel graphene wrapping approach of Ni@Fe2O3 superparticles, which can be extended as a concept approach for other nanomaterials as well. It uses sulfonated reduced graphene oxide, but avoids thermal treatments and use of toxic agents like hydrazine for its reduction. The modification of graphene oxide is achieved by the introduction of sulfate groups accompanied with reduction and elimination reactions, due to the treatment with oleum. The successful wrapping of nanoparticles is proven by energy dispersive X-ray spectroscopy, high-resolution transmission electron microscopy and Raman spectroscopy. The developed composite material shows strongly improved performance as anode material in lithium-ion batteries (compared to unwrapped Ni@Fe2O3) as it offers a reversible capacity of 1051mAhg(-1) after 40 cycles at C/20, compared with 460mAhg(-1) for unwrapped Ni@Fe2O3. The C rate capability is also improved by the wrapping approach, as specific capacities for wrapped particles are about twice of those offered by unwrapped particles. Additionally, the benefit for the use of the advanced superparticle morphology is demonstrated by comparing wrapped Ni@Fe2O3 particles with wrapped Fe2O3 nanorice. PMID:27295319

  17. Observation of the Fe—CN and Fe—CO Vibrations in the Active Site of [NiFe] Hydrogenase by Nuclear Resonance Vibrational Spectroscopy**

    PubMed Central

    Kamali, Saeed; Wang, Hongxin; Mitra, Devrani; Ogata, Hideaki; Manor, Brian C.; Rauchfuss, Thomas B.; Byrne, Deborah; Bonnefoy, Violaine; Jenney, Francis E.; Adams, Michael W. W.; Yoda, Yoshitaka; Alp, Ercan; Zhao, Jiyong; Cramer, Stephen P.

    2012-01-01

    Nuclear inelastic scattering of 57Fe labeled [NiFe] hydrogenase is shown to give information on different states of the enzyme. It was thus possible to detect and assign Fe–CO and Fe–CN bending and stretching vibrations of the active site outside the spectral range of the Fe–S cluster normal modes. PMID:23136119

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

    SciTech Connect

    Castro, I. L.; Nascimento, V. P.; Passamani, E. C.; Takeuchi, A. Y.; Larica, C.; Tafur, M.; Pelegrini, F.

    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 for 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.

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

    PubMed

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

    2016-04-25

    [NiFe] hydrogenases are metalloenzymes catalyzing the reversible heterolytic cleavage of hydrogen into protons and electrons. Gas tunnels make the deeply buried active site accessible to substrates and inhibitors. Understanding the architecture and function of the tunnels is pivotal to modulating the feature of O2 tolerance in a subgroup of these [NiFe] hydrogenases, as they are interesting for developments in renewable energy technologies. Here we describe the crystal structure of the O2 -tolerant membrane-bound [NiFe] hydrogenase of Ralstonia eutropha (ReMBH), using krypton-pressurized crystals. The positions of the krypton atoms allow a comprehensive description of the tunnel network within the enzyme. A detailed overview of tunnel sizes, lengths, and routes is presented from tunnel calculations. A comparison of the ReMBH tunnel characteristics with crystal structures of other O2 -tolerant and O2 -sensitive [NiFe] hydrogenases revealed considerable differences in tunnel size and quantity between the two groups, which might be related to the striking feature of O2 tolerance. PMID:26913499

  20. Facile hybridization of Ni@Fe2O3 superparticles with functionalized reduced graphene oxide and its application as anode material in lithium-ion batteries.

    PubMed

    Backert, Gregor; Oschmann, Bernd; Tahir, Muhammad Nawaz; Mueller, Franziska; Lieberwirth, Ingo; Balke, Benjamin; Tremel, Wolfgang; Passerini, Stefano; Zentel, Rudolf

    2016-09-15

    In our present work we developed a novel graphene wrapping approach of Ni@Fe2O3 superparticles, which can be extended as a concept approach for other nanomaterials as well. It uses sulfonated reduced graphene oxide, but avoids thermal treatments and use of toxic agents like hydrazine for its reduction. The modification of graphene oxide is achieved by the introduction of sulfate groups accompanied with reduction and elimination reactions, due to the treatment with oleum. The successful wrapping of nanoparticles is proven by energy dispersive X-ray spectroscopy, high-resolution transmission electron microscopy and Raman spectroscopy. The developed composite material shows strongly improved performance as anode material in lithium-ion batteries (compared to unwrapped Ni@Fe2O3) as it offers a reversible capacity of 1051mAhg(-1) after 40 cycles at C/20, compared with 460mAhg(-1) for unwrapped Ni@Fe2O3. The C rate capability is also improved by the wrapping approach, as specific capacities for wrapped particles are about twice of those offered by unwrapped particles. Additionally, the benefit for the use of the advanced superparticle morphology is demonstrated by comparing wrapped Ni@Fe2O3 particles with wrapped Fe2O3 nanorice.

  1. Electrokinetic properties of PMAA functionalized NiFe2O4 nanoparticles synthesized by thermal plasma route

    NASA Astrophysics Data System (ADS)

    Bhosale, Shivaji V.; Mhaske, Pravin; Kanhe, N.; Navale, A. B.; Bhoraskar, S. V.; Mathe, V. L.; Bhatt, S. K.

    2014-04-01

    The magnetic nickel ferrite (NiFe2O4) nanoparticles with an average size of 30nm were synthesised by Transferred arc DC Thermal Plasma route. The synthesized nickel ferrite nanoparticles were characterized by TEM and FTIR techniques. The synthesized nickel ferrite nanoparticles were further functionalized with PMAA (polymethacrylic acid) by self emulsion polymerization method and subsequently were characterized by FTIR and Zeta Analyzer. The variation of zeta potential with pH was systematically studied for both PMAA functionalized (PNFO) and uncoated nickel ferrite nanoparticles (NFO). The IEP (isoelectric points) for PNFO and NFO was determined from the graph of zeta potential vs pH. It was observed that the IEP for NFO was at 7.20 and for PNFO it was 2.52. The decrease in IEP of PNFO was attributed to the COOH functional group of PMAA.

  2. Introduction and pinning of domain walls in 50 nm NiFe constrictions using local and external magnetic fields

    NASA Astrophysics Data System (ADS)

    Zahnd, G.; Pham, V. T.; Marty, A.; Jamet, M.; Beigné, C.; Notin, L.; Vergnaud, C.; Rortais, F.; Vila, L.; Attané, J.-P.

    2016-05-01

    We study domain wall injection in 100 nm wide NiFe nanowires, followed by domain wall propagation and pinning on 50 nm wide constrictions. The injection is performed using local and external magnetic fields. Using several nucleation pad geometries, we show that at these small dimensions the use of an external field only does not allow obtaining a reproducible injection/pinning process. However, the use of an additional local field, created by an Oersted line, allows to nucleate a reversed domain at zero external applied field. Then, an external field of 5 mT enables the domain wall to propagate far from the Oersted line, and the pinning occurs reproducibly. We also show that notwithstanding the reproducibility of the pinning process, the depinning field is found to be stochastic, following a bimodal distribution. Using micromagnetic simulation we link two different DW configurations, vortex and transverse, to the two typical depinning fields.

  3. Anomalous magnetic behavior in nanocomposite materials of reduced graphene oxide-Ni/NiFe{sub 2}O{sub 4}

    SciTech Connect

    Kollu, Pratap E-mail: anirmalagrace@vit.ac.in; Prathapani, Sateesh; Varaprasadarao, Eswara K.; Mallick, Sudhanshu; Bahadur, D. E-mail: anirmalagrace@vit.ac.in; Santosh, Chella; Grace, Andrews Nirmala E-mail: anirmalagrace@vit.ac.in

    2014-08-04

    Magnetic Reduced Graphene Oxide-Nickel/NiFe{sub 2}O{sub 4} (RGO-Ni/NF) nanocomposite has been synthesized by one pot solvothermal method. Respective phase formations and their purities in the composite are confirmed by High Resolution Transmission Electron Microscope and X Ray Diffraction, respectively. For the RGO-Ni/NF composite material finite-size effects lead to the anomalous magnetic behavior, which is corroborated in temperature and field dependent magnetization curves. Here, we are reporting the behavior of higher magnetization values for Zero Field Cooled condition to that of Field Cooled for the RGO-Ni/NF nanocomposite. Also, the observed negative and positive moments in Hysteresis loops at relatively smaller applied fields (100 Oe and 200 Oe) are explained on the basis of surface spin disorder.

  4. Tunneling conductance studies in the ion-beam sputtered CoFe/Mg/MgO/NiFe magnetic tunnel junctions

    SciTech Connect

    Singh, Braj Bhusan; Chaudhary, Sujeet

    2013-06-03

    Magnetic tunnel junctions consisting of CoFe(10 nm)/Mg(1 nm)/MgO(3.5 nm)/NiFe(10 nm) are grown at room temperature using dual ion beam sputtering via in-situ shadow masking. The effective barrier thickness and average barrier height are estimated to be 3.5 nm (2.9 nm) and 0.69 eV (1.09 eV) at 290 K (70 K), respectively. The tunnel magnetoresistance value of 0.2 % and 2.3 % was observed at 290 K and 60 K, respectively. The temperature dependence of tunneling conductance revealed the presence of localized states present within the forbidden gap of the MgO barrier leading to finite inelastic spin independent tunneling contributions, which degrade the TMR value.

  5. Modulation of Active Site Electronic Structure by the Protein Matrix to Control [NiFe] Hydrogenase Reactivity

    SciTech Connect

    Smith, Dayle MA; Raugei, Simone; Squier, Thomas C.

    2014-09-30

    Control of the reactivity of the nickel center of the [NiFe] hydrogenase and other metalloproteins commonly involves outer coordination sphere ligands that act to modify the geometry and physical properties of the active site metal centers. We carried out a combined set of classical molecular dynamics and quantum/classical mechanics calculations to provide quantitative estimates of how dynamic fluctuations of the active site within the protein matrix modulate the electronic structure at the catalytic center. Specifically we focused on the dynamics of the inner and outer coordination spheres of the cysteinate-bound Ni–Fe cluster in the catalytically active Ni-C state. There are correlated movements of the cysteinate ligands and the surrounding hydrogen-bonding network, which modulate the electron affinity at the active site and the proton affinity of a terminal cysteinate. On the basis of these findings, we hypothesize a coupling between protein dynamics and electron and proton transfer reactions critical to dihydrogen production.

  6. Control of domain wall pinning by localised focused Ga {sup +} ion irradiation on Au capped NiFe nanowires

    SciTech Connect

    Burn, D. M. Atkinson, D.

    2014-10-28

    Understanding domain wall pinning and propagation in nanowires are important for future spintronics and nanoparticle manipulation technologies. Here, the effects of microscopic local modification of the magnetic properties, induced by focused-ion-beam intermixing, in NiFe/Au bilayer nanowires on the pinning behavior of domain walls was investigated. The effects of irradiation dose and the length of the irradiated features were investigated experimentally. The results are considered in the context of detailed quasi-static micromagnetic simulations, where the ion-induced modification was represented as a local reduction of the saturation magnetization. Simulations show that domain wall pinning behavior depends on the magnitude of the magnetization change, the length of the modified region, and the domain wall structure. Comparative analysis indicates that reduced saturation magnetisation is not solely responsible for the experimentally observed pinning behavior.

  7. Enhanced Oxygen-Tolerance of the Full Heterotrimeric Membrane-Bound [NiFe]-Hydrogenase of Ralstonia eutropha

    PubMed Central

    2014-01-01

    Hydrogenases are oxygen-sensitive enzymes that catalyze the conversion between protons and hydrogen. Water-soluble subcomplexes of membrane-bound [NiFe]-hydrogenases (MBH) have been extensively studied for applications in hydrogen–oxygen fuel cells as they are relatively tolerant to oxygen, although even these catalysts are still inactivated in oxidative conditions. Here, the full heterotrimeric MBH of Ralstonia eutropha, including the membrane-integral cytochrome b subunit, was investigated electrochemically using electrodes modified with planar tethered bilayer lipid membranes (tBLM). Cyclic voltammetry and chronoamperometry experiments show that MBH, in equilibrium with the quinone pool in the tBLM, does not anaerobically inactivate under oxidative redox conditions. In aerobic environments, the MBH is reversibly inactivated by O2, but reactivation was found to be fast even under oxidative redox conditions. This enhanced resistance to inactivation is ascribed to the oligomeric state of MBH in the lipid membrane. PMID:24866391

  8. Rubredoxin-related Maturation Factor Guarantees Metal Cofactor Integrity during Aerobic Biosynthesis of Membrane-bound [NiFe] Hydrogenase*

    PubMed Central

    Fritsch, Johannes; Siebert, Elisabeth; Priebe, Jacqueline; Zebger, Ingo; Lendzian, Friedhelm; Teutloff, Christian; Friedrich, Bärbel; Lenz, Oliver

    2014-01-01

    The membrane-bound [NiFe] hydrogenase (MBH) supports growth of Ralstonia eutropha H16 with H2 as the sole energy source. The enzyme undergoes a complex biosynthesis process that proceeds during cell growth even at ambient O2 levels and involves 14 specific maturation proteins. One of these is a rubredoxin-like protein, which is essential for biosynthesis of active MBH at high oxygen concentrations but dispensable under microaerobic growth conditions. To obtain insights into the function of HoxR, we investigated the MBH protein purified from the cytoplasmic membrane of hoxR mutant cells. Compared with wild-type MBH, the mutant enzyme displayed severely decreased hydrogenase activity. Electron paramagnetic resonance and infrared spectroscopic analyses revealed features resembling those of O2-sensitive [NiFe] hydrogenases and/or oxidatively damaged protein. The catalytic center resided partially in an inactive Niu-A-like state, and the electron transfer chain consisting of three different Fe-S clusters showed marked alterations compared with wild-type enzyme. Purification of HoxR protein from its original host, R. eutropha, revealed only low protein amounts. Therefore, recombinant HoxR protein was isolated from Escherichia coli. Unlike common rubredoxins, the HoxR protein was colorless, rather unstable, and essentially metal-free. Conversion of the atypical iron-binding motif into a canonical one through genetic engineering led to a stable reddish rubredoxin. Remarkably, the modified HoxR protein did not support MBH-dependent growth at high O2. Analysis of MBH-associated protein complexes points toward a specific interaction of HoxR with the Fe-S cluster-bearing small subunit. This supports the previously made notion that HoxR avoids oxidative damage of the metal centers of the MBH, in particular the unprecedented Cys6[4Fe-3S] cluster. PMID:24448806

  9. Dual role of HupF in the biosynthesis of [NiFe] hydrogenase in Rhizobium leguminosarum

    PubMed Central

    2012-01-01

    Background [NiFe] hydrogenases are enzymes that catalyze the oxidation of hydrogen into protons and electrons, to use H2 as energy source, or the production of hydrogen through proton reduction, as an escape valve for the excess of reduction equivalents in anaerobic metabolism. Biosynthesis of [NiFe] hydrogenases is a complex process that occurs in the cytoplasm, where a number of auxiliary proteins are required to synthesize and insert the metal cofactors into the enzyme structural units. The endosymbiotic bacterium Rhizobium leguminosarum requires the products of eighteen genes (hupSLCDEFGHIJKhypABFCDEX) to synthesize an active hydrogenase. hupF and hupK genes are found only in hydrogenase clusters from bacteria expressing hydrogenase in the presence of oxygen. Results HupF is a HypC paralogue with a similar predicted structure, except for the C-terminal domain present only in HupF. Deletion of hupF results in the inability to process the hydrogenase large subunit HupL, and also in reduced stability of this subunit when cells are exposed to high oxygen tensions. A ΔhupF mutant was fully complemented for hydrogenase activity by a C-terminal deletion derivative under symbiotic, ultra low-oxygen tensions, but only partial complementation was observed in free living cells under higher oxygen tensions (1% or 3%). Co-purification experiments using StrepTag-labelled HupF derivatives and mass spectrometry analysis indicate the existence of a major complex involving HupL and HupF, and a less abundant HupF-HupK complex. Conclusions The results indicate that HupF has a dual role during hydrogenase biosynthesis: it is required for hydrogenase large subunit processing and it also acts as a chaperone to stabilize HupL when hydrogenase is synthesized in the presence of oxygen. PMID:23136881

  10. X-ray crystallographic and computational studies of the O2-tolerant [NiFe]-hydrogenase 1 from Escherichia coli.

    PubMed

    Volbeda, Anne; Amara, Patricia; Darnault, Claudine; Mouesca, Jean-Marie; Parkin, Alison; Roessler, Maxie M; Armstrong, Fraser A; Fontecilla-Camps, Juan C

    2012-04-01

    The crystal structure of the membrane-bound O(2)-tolerant [NiFe]-hydrogenase 1 from Escherichia coli (EcHyd-1) has been solved in three different states: as-isolated, H(2)-reduced, and chemically oxidized. As very recently reported for similar enzymes from Ralstonia eutropha and Hydrogenovibrio marinus, two supernumerary Cys residues coordinate the proximal [FeS] cluster in EcHyd-1, which lacks one of the inorganic sulfide ligands. We find that the as-isolated, aerobically purified species contains a mixture of at least two conformations for one of the cluster iron ions and Glu76. In one of them, Glu76 and the iron occupy positions that are similar to those found in O(2)-sensitive [NiFe]-hydrogenases. In the other conformation, this iron binds, besides three sulfur ligands, the amide N from Cys20 and one Oε of Glu76. Our calculations show that oxidation of this unique iron generates the high-potential form of the proximal cluster. The structural rearrangement caused by oxidation is confirmed by our H(2)-reduced and oxidized EcHyd-1 structures. Thus, thanks to the peculiar coordination of the unique iron, the proximal cluster can contribute two successive electrons to secure complete reduction of O(2) to H(2)O at the active site. The two observed conformations of Glu76 are consistent with this residue playing the role of a base to deprotonate the amide moiety of Cys20 upon iron binding and transfer the resulting proton away, thus allowing the second oxidation to be electroneutral. The comparison of our structures also shows the existence of a dynamic chain of water molecules, resulting from O(2) reduction, located near the active site. PMID:22431599

  11. In search of metal hydrides: an X-ray absorption and emission study of [NiFe] hydrogenase model complexes.

    PubMed

    Hugenbruch, Stefan; Shafaat, Hannah S; Krämer, Tobias; Delgado-Jaime, Mario Ulises; Weber, Katharina; Neese, Frank; Lubitz, Wolfgang; DeBeer, Serena

    2016-04-28

    Metal hydrides are invoked as important intermediates in both chemical and biological H2 production. In the [NiFe] hydrogenase enzymes, pulsed EPR and high-resolution crystallography have argued that the hydride interacts primarily at the Ni site. In contrast, in [NiFe] hydrogenase model complexes, it is observed that the bridging hydride interacts primarily with the Fe. Herein, we utilize a combination of Ni and Fe X-ray absorption (XAS) and emission (XES) spectroscopies to examine the contribution of the bridging hydride to the observed spectral features in [(dppe)Ni(μ-pdt)(μ-H)Fe(CO)3](+). The corresponding data on (dppe)Ni(μ-pdt)Fe(CO)3 are used as a reference for the changes that occur in the absence of a hydride bridge. For further interpretation of the observed spectral features, all experimental spectra were calculated using a density functional theory (DFT) approach, with excellent agreement between theory and experiment. It is found that the iron valence-to-core (VtC) XES spectra reveal clear signatures for the presence of a Fe-H interaction in the hydride bridged model complex. In contrast, the Ni VtC XES spectrum largely reflects changes in the local Ni geometry and shows little contribution from a Ni-H interaction. A stepwise theoretical analysis of the hydride contribution and the Ni site symmetry provides insights into the factors, which govern the different metal-hydride interactions in both the model complexes and the enzyme. Furthermore, these results establish the utility of two-color XES to reveal important insights into the electronic structure of various metal-hydride species. PMID:26924248

  12. Oxygen Evolution Reaction Dynamics, Faradaic Charge Efficiency, and the Active Metal Redox States of Ni-Fe Oxide Water Splitting Electrocatalysts.

    PubMed

    Görlin, Mikaela; Chernev, Petko; Ferreira de Araújo, Jorge; Reier, Tobias; Dresp, Sören; Paul, Benjamin; Krähnert, Ralph; Dau, Holger; Strasser, Peter

    2016-05-01

    Mixed Ni-Fe oxides are attractive anode catalysts for efficient water splitting in solar fuels reactors. Because of conflicting past reports, the catalytically active metal redox state of the catalyst has remained under debate. Here, we report an in operando quantitative deconvolution of the charge injected into the nanostructured Ni-Fe oxyhydroxide OER catalysts or into reaction product molecules. To achieve this, we explore the oxygen evolution reaction dynamics and the individual faradaic charge efficiencies using operando differential electrochemical mass spectrometry (DEMS). We further use X-ray absorption spectroscopy (XAS) under OER conditions at the Ni and Fe K-edges of the electrocatalysts to evaluate oxidation states and local atomic structure motifs. DEMS and XAS data consistently reveal that up to 75% of the Ni centers increase their oxidation state from +2 to +3, while up to 25% arrive in the +4 state for the NiOOH catalyst under OER catalysis. The Fe centers consistently remain in the +3 state, regardless of potential and composition. For mixed Ni100-xFex catalysts, where x exceeds 9 atomic %, the faradaic efficiency of O2 sharply increases from ∼30% to 90%, suggesting that Ni atoms largely remain in the oxidation state +2 under catalytic conditions. To reconcile the apparent low level of oxidized Ni in mixed Ni-Fe catalysts, we hypothesize that a kinetic competition between the (i) metal oxidation process and the (ii) metal reduction step during O2 release may account for an insignificant accumulation of detectable high-valent metal states if the reaction rate of process (ii) outweighs that of (i). We conclude that a discussion of the superior catalytic OER activity of Ni-FeOOH electrocatalysts in terms of surface catalysis and redox-inactive metal sites likely represents an oversimplification that fails to capture essential aspects of the synergisms at highly active Ni-Fe sites.

  13. A Facile Molten-Salt Route for Large-Scale Synthesis of NiFe2O4 Nanoplates with Enhanced Lithium Storage Capability.

    PubMed

    Huang, Gang; Du, Xinchuan; Zhang, Feifei; Yin, Dongming; Wang, Limin

    2015-09-28

    Binary metal oxides have been deemed as a promising class of electrode materials for high-performance lithium ion batteries owing to their higher conductivity and electrochemical activity than corresponding monometal oxides. Here, NiFe2O4 nanoplates consisting of nanosized building blocks have been successfully fabricated by a facile, large-scale NaCl and KCl molten-salt route, and the changes in the morphology of NiFe2O4 as a function of the molten-salt amount have been systemically investigated. The results indicate that the molten-salt amount mainly influences the diameter and thickness of the NiFe2O4 nanoplates as well as the morphology of the nanosized building blocks. Cyclic voltammetry (CV) and galvanostatic charge-discharge measurements have been conducted to evaluate the lithium storage properties of the NiFe2O4 nanoplates prepared with a Ni(NO3)2/Fe(NO3)3/KCl/NaCl molar ratio of 1:2:20:60. A high reversible capacity of 888 mAh g(-1) is delivered over 100 cycles at a current density of 100 mA g(-1). Even at a current density of 5000 mA g(-1) , the discharge capacity could still reach 173 mAh g(-1). Such excellent electrochemical performances of the NiFe2O4 nanoplates are contributed to the short Li(+) diffusion distance of the nanosized building blocks and the synergetic effect of the Ni(2+) and Fe(3+) ions.

  14. Tunable magnetocaloric effect in transition metal alloys.

    PubMed

    Belyea, Dustin D; Lucas, M S; Michel, E; Horwath, J; Miller, Casey W

    2015-01-01

    The unpredictability of geopolitical tensions and resulting supply chain and pricing instabilities make it imperative to explore rare earth free magnetic materials. As such, we have investigated fully transition metal based "high entropy alloys" in the context of the magnetocaloric effect. We find the NiFeCoCrPdx family exhibits a second order magnetic phase transition whose critical temperature is tunable from 100 K to well above room temperature. The system notably displays changes in the functionality of the magnetic entropy change depending on x, which leads to nearly 40% enhancement of the refrigerant capacity. A detailed statistical analysis of the universal scaling behavior provides direct evidence that heat treatment and Pd additions reduce the distribution of exchange energies in the system, leading to a more magnetically homogeneous alloy. The general implications of this work are that the parent NiFeCoCr compound can be tuned dramatically with FCC metal additives. Together with their relatively lower cost, their superior mechanical properties that aid manufacturability and their relative chemical inertness that aids product longevity, NiFeCoCr-based materials could ultimately lead to commercially viable magnetic refrigerants. PMID:26507636

  15. Magneto-structural studies of sol-gel synthesized nanocrystalline manganese substituted nickel ferrites

    NASA Astrophysics Data System (ADS)

    Pandav, R. S.; Patil, R. P.; Chavan, S. S.; Mulla, I. S.; Hankare, P. P.

    2016-11-01

    Nanocrystalline NiFe2-xMnxO4 (2≥x≥0) ferrites were prepared by sol-gel method. X-ray diffraction patterns reveal that synthesized compounds are in single phase cubic spinel lattice for all the composition. The surface morphology of all the samples were studied by scanning electron microscopy. The particle size measured from transmission electron microscopy and X-ray diffraction patterns confirms the nanosized dimension of the as-prepared powder. The elemental analysis was carried out by energy dispersive X-ray analysis technique. Magnetic properties such as saturation magnetization, coercivity and remanence are studied as a function of increasing Mn concentration at room temperature. The saturation magnetization shows a decreasing trend with increase in Mn content. The substitution of manganese in the nickel ferrite affects the structural and magnetic properties of cubic spinels.

  16. STRUCTURE AND MAGNETIC PROPERTIES OF NANOCRYSTALLINE (Fe50Co50)73.5Cu1Nb3Si13.5B9 ALLOYS

    NASA Astrophysics Data System (ADS)

    Wang, Yuxin; Ju, Ying; Lu, Wei; Yan, Biao; Gao, Wei

    2013-07-01

    (Fe50Co50)73.5Cu1Nb3Si13.5B9 amorphous ribbons, a type of Co doped Finemet alloy, were prepared by melt-spinning and annealed at 440-560°C for 30 min. Influences of heat treatment and Co content on the crystallization were analyzed through differential scanning calorimetric (DSC) and X-ray diffractometry (XRD). The microstructure was analyzed by atomic force microscopy (AFM). The magnetic properties of (Fe50Co50)73.5Cu1Nb3Si13.5B9 and Finemet ribbons were tested by an alternating current soft magnetic properties measurement system. A comparative study of frequency dispersion properties between (Fe50Co50)73.5Cu1Nb3Si13.5B9 and Finemet was conducted. Results indicate that the optimal magnetic property has been achieved when (Fe50Co50)73.5Cu1Nb3Si13.5B9 ribbons were annealed at the temperature range of 480°C-520°C, after which the grain size became between 10 nm and 20 nm. Although the permeability of (Fe50Co50)73.5Cu1Nb3Si13.5B9 is not as high as that of Finemet, this Co-doped Finemet amorphous alloy presents better high frequency properties, and therefore is a promising candidate for the high frequency field applications.

  17. Hydrogenation thermodynamics of melt-spun magnesium rich Mg-Ni nanocrystalline alloys with the addition of multiwalled carbon nanotubes and TiF3

    NASA Astrophysics Data System (ADS)

    Hou, Xiaojiang; Hu, Rui; Zhang, Tiebang; Kou, Hongchao; Li, Jinshan

    2016-02-01

    Based on the complexity of hydrogen absorption/desorption process and from the perspective of overall control, the as-cast Mg-10wt%Ni (Mg10Ni) alloy has been successively optimized by melt-spinning and surface catalyzed to realize the internal refinement as well as surface modification. The isothermal hydrogenation behavior of modified Mg-rich alloys has been investigated in this work. The results indicate that melt-spun Mg10Ni catalyzed by multiwalled carbon nanotubes (MWCNTs) coupling with TiF3 possesses superior activation properties and can absorb 6.23 wt% at 250 °C under 2.5 MPa. It is worth mentioning that the hydrogenation capacities of Mg10Ni-MWCNTs-TiF3 are 5.93 wt% and 5.99 wt% within the initial 1 min and 5 min, respectively. Meanwhile, the catalytic effect of MWCNTs and TiF3 has been discussed. The improved activation performance as well as the thermodynamics properties of Mg10Ni catalyzed by MWCNTs and TiF3 is attributed to the synergistic effect on dissociation of H2 molecules, diffusion of H-atoms and heterogeneous nucleation of hydrides.

  18. Alloy

    NASA Astrophysics Data System (ADS)

    Cabeza, Sandra; Garcés, Gerardo; Pérez, Pablo; Adeva, Paloma

    2014-07-01

    The Mg98.5Gd1Zn0.5 alloy produced by a powder metallurgy route was studied and compared with the same alloy produced by extrusion of ingots. Atomized powders were cold compacted and extruded at 623 K and 673 K (350 °C and 400 °C). The microstructure of extruded materials was characterized by α-Mg grains, and Mg3Gd and 14H-LPSO particles located at grain boundaries. Grain size decreased from 6.8 μm in the extruded ingot, down to 1.6 μm for powders extruded at 623 K (350 °C). Grain refinement resulted in an increase in mechanical properties at room and high temperatures. Moreover, at high temperatures the PM alloy showed superplasticity at high strain rates, with elongations to failure up to 700 pct.

  19. Modeling of the Site Preference in Ternary B2-Ordered Ni-Al-Fe Alloys

    NASA Technical Reports Server (NTRS)

    Bozzolo, Guillermo H.; Khalil, Joseph; Noebe, Ronald D.

    2002-01-01

    The underlying equilibrium structure, site substitution behavior, and lattice parameter of ternary Ni-Fe-Al alloys are determined via Monte Carlo-Metropolis computer simulations and analytical calculations using the BFS method for alloys for the energetics. As a result of the theoretical calculations presented, a simple approach based on the energetics of small atomic clusters is introduced to explain the observed site preference schemes.

  20. Nano-crystalline P/M aluminium for automotive applications

    NASA Astrophysics Data System (ADS)

    Hummert, K.; Schattevoy, R.; Broda, M.; Knappe, M.; Beiss, P.; Klubberg, F.; Schubert, T. H.; Leuschner, R.

    2009-01-01

    The reduction of total vehicle weight and lowering of moving masses within the engine are key elements to overcome future emission challenges of the automotive industry. Within a German BMBF funded project the melt spinning technology will be driven to a series production status. The very fast cooling condition of the melt leads to a nano-structure of the aluminium material. This results in new material properties of known alloys. The strength increases dramatically without lowered forming behaviour. With this process the freedom of designing complex alloys is very flexible. Different alloys have been investigated for several applications, where high strength at room and elevated temperatures and/or high wear resistance is required. This paper presents some results regarding the processing, microstructure and mechanical properties of a developed Al-Ni-Fe alloy. This joined research project with partners from the automotive industry as well as automotive suppliers and universities is funded by the German BMBF "NanoMobile" Program under Project number 03X3008.

  1. Thermodynamic analysis of binary Fe{sub 85}B{sub 15} to quinary Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloys for primary crystallizations of α-Fe in nanocrystalline soft magnetic alloys

    SciTech Connect

    Takeuchi, A. Zhang, Y.; Takenaka, K.; Makino, A.

    2015-05-07

    Fe-based Fe{sub 85}B{sub 15}, Fe{sub 84}B{sub 15}Cu{sub 1}, Fe{sub 82}Si{sub 2}B{sub 15}Cu{sub 1}, Fe{sub 85}Si{sub 2}B{sub 12}Cu{sub 1}, and Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} (NANOMET{sup ®}) alloys were experimental and computational analyzed to clarify the features of NANOMET that exhibits high saturation magnetic flux density (B{sub s}) nearly 1.9 T and low core loss than conventional nanocrystalline soft magnetic alloys. The X-ray diffraction analysis for ribbon specimens produced experimentally by melt spinning from melts revealed that the samples were almost formed into an amorphous single phase. Then, the as-quenched samples were analyzed with differential scanning calorimeter (DSC) experimentally for exothermic enthalpies of the primary and secondary crystallizations (ΔH{sub x1} and ΔH{sub x2}) and their crystallization temperatures (T{sub x1} and T{sub x2}), respectively. The ratio ΔH{sub x1}/ΔH{sub x2} measured by DSC experimentally tended to be extremely high for the Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloy, and this tendency was reproduced by the analysis with commercial software, Thermo-Calc, with database for Fe-based alloys, TCFE7 for Gibbs free energy (G) assessments. The calculations exhibit that a volume fraction (V{sub f}) of α-Fe tends to increase from 0.56 for the Fe{sub 85}B{sub 15} to 0.75 for the Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloy. The computational analysis of the alloys for G of α-Fe and amorphous phases (G{sub α-Fe} and G{sub amor}) shows that a relationship G{sub α-Fe} ∼ G{sub amor} holds for the Fe{sub 85}Si{sub 2}B{sub 12}Cu{sub 1}, whereas G{sub α-Fe} < G{sub amor} for the Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloy at T{sub x1} and that an extremely high V{sub f} = 0.75 was achieved for the Fe{sub 85}Si{sub 2}B{sub 8}P{sub 4}Cu{sub 1} alloy by including 2.8 at. % Si and 4.5 at. % P into α-Fe. These computational results indicate that the Fe{sub 85}Si{sub 2}B

  2. Gas phase hydrogen permeation in a Ni-Fe-Co superalloy

    SciTech Connect

    Shanabarger, M.R. )

    1993-05-01

    Incoloy 909 is a high temperature alloy being considered for use in advanced aerospace engines where it will be in contact with high temperature gaseous hydrogen. In the present study, hydrogen permeation measurements were made for Incoloy 909 using a membrane' technique, where gaseous hydrogen at the entrance side of a thin membrane is transported trough the bulk to the exit side of the membrane. The present measurements were made over the temperature range from 400 C to 810 C and the pressure range from 2.7 [times] 10[sup 3] N/m[sup 2] to 1.3 [times] 10[sup 5] N/m[sup 2]. The present work is compared with the earlier results obtained by Robertson for Incoloy 903.

  3. Removal of Rhodamine B from aqueous solution using magnetic NiFe nanoparticles.

    PubMed

    Liu, Yan; Liu, Kaige; Zhang, Lin; Zhang, Zhaowen

    2015-01-01

    Surface-modified magnetic nano alloy particles Ni2.33Fe were prepared using a hydrothermal method and they were utilized for removing Rhodamine B (RhB) from aqueous solution. The magnetic nanoparticles were characterized by X-ray diffraction, scanning electron microscopy, thermogravimetric analysis and Fourier transform infrared spectroscopy, which confirmed that the surface of the magnetic product with a face-centered cubic-type structure was successfully modified by sodium citrate. Kinetics studies were conducted. The pseudo-second-order kinetic model was used for fitting the kinetic data successfully. The Freundlich and Langmuir adsorption models were employed for the mathematical description of adsorption equilibrium. It was found that the adsorption isotherm can be very satisfactorily fitted by the Freundlich model.

  4. Process for fabricating articles of tungsten-nickel-iron alloy

    DOEpatents

    Northcutt, Jr., Walter G.; Snyder, Jr., William B.

    1976-01-01

    A high density W--Ni--Fe alloy of composition 85-96% by weight W and the remainder Ni and Fe in a wt. ratio of 5:5-8:2 having enhanced mechanical properties is prepared by compacting the mixed powders, sintering the compact in reducing atmosphere to near theoretical density followed by further sintering at a temperature where a liquid phase is present, vacuum annealing, and cold working to achieve high uniform hardness.

  5. Temperature variations at nano-scale level in phase transformed nanocrystalline NiTi shape memory alloys adjacent to graphene layers.

    PubMed

    Amini, Abbas; Cheng, Chun; Naebe, Minoo; Church, Jeffrey S; Hameed, Nishar; Asgari, Alireza; Will, Frank

    2013-07-21

    The detection and control of the temperature variation at the nano-scale level of thermo-mechanical materials during a compression process have been challenging issues. In this paper, an empirical method is proposed to predict the temperature at the nano-scale level during the solid-state phase transition phenomenon in NiTi shape memory alloys. Isothermal data was used as a reference to determine the temperature change at different loading rates. The temperature of the phase transformed zone underneath the tip increased by ∼3 to 40 °C as the loading rate increased. The temperature approached a constant with further increase in indentation depth. A few layers of graphene were used to enhance the cooling process at different loading rates. Due to the presence of graphene layers the temperature beneath the tip decreased by a further ∼3 to 10 °C depending on the loading rate. Compared with highly polished NiTi, deeper indentation depths were also observed during the solid-state phase transition, especially at the rate dependent zones. Larger superelastic deformations confirmed that the latent heat transfer through the deposited graphene layers allowed a larger phase transition volume and, therefore, more stress relaxation and penetration depth. PMID:23744099

  6. Temperature variations at nano-scale level in phase transformed nanocrystalline NiTi shape memory alloys adjacent to graphene layers

    NASA Astrophysics Data System (ADS)

    Amini, Abbas; Cheng, Chun; Naebe, Minoo; Church, Jeffrey S.; Hameed, Nishar; Asgari, Alireza; Will, Frank

    2013-06-01

    The detection and control of the temperature variation at the nano-scale level of thermo-mechanical materials during a compression process have been challenging issues. In this paper, an empirical method is proposed to predict the temperature at the nano-scale level during the solid-state phase transition phenomenon in NiTi shape memory alloys. Isothermal data was used as a reference to determine the temperature change at different loading rates. The temperature of the phase transformed zone underneath the tip increased by ~3 to 40 °C as the loading rate increased. The temperature approached a constant with further increase in indentation depth. A few layers of graphene were used to enhance the cooling process at different loading rates. Due to the presence of graphene layers the temperature beneath the tip decreased by a further ~3 to 10 °C depending on the loading rate. Compared with highly polished NiTi, deeper indentation depths were also observed during the solid-state phase transition, especially at the rate dependent zones. Larger superelastic deformations confirmed that the latent heat transfer through the deposited graphene layers allowed a larger phase transition volume and, therefore, more stress relaxation and penetration depth.

  7. Temperature variations at nano-scale level in phase transformed nanocrystalline NiTi shape memory alloys adjacent to graphene layers.

    PubMed

    Amini, Abbas; Cheng, Chun; Naebe, Minoo; Church, Jeffrey S; Hameed, Nishar; Asgari, Alireza; Will, Frank

    2013-07-21

    The detection and control of the temperature variation at the nano-scale level of thermo-mechanical materials during a compression process have been challenging issues. In this paper, an empirical method is proposed to predict the temperature at the nano-scale level during the solid-state phase transition phenomenon in NiTi shape memory alloys. Isothermal data was used as a reference to determine the temperature change at different loading rates. The temperature of the phase transformed zone underneath the tip increased by ∼3 to 40 °C as the loading rate increased. The temperature approached a constant with further increase in indentation depth. A few layers of graphene were used to enhance the cooling process at different loading rates. Due to the presence of graphene layers the temperature beneath the tip decreased by a further ∼3 to 10 °C depending on the loading rate. Compared with highly polished NiTi, deeper indentation depths were also observed during the solid-state phase transition, especially at the rate dependent zones. Larger superelastic deformations confirmed that the latent heat transfer through the deposited graphene layers allowed a larger phase transition volume and, therefore, more stress relaxation and penetration depth.

  8. Models of the Ni-L and Ni-SIa States of the [NiFe]-Hydrogenase Active Site.

    PubMed

    Chambers, Geoffrey M; Huynh, Mioy T; Li, Yulong; Hammes-Schiffer, Sharon; Rauchfuss, Thomas B; Reijerse, Edward; Lubitz, Wolfgang

    2016-01-19

    A new class of synthetic models for the active site of [NiFe]-hydrogenases are described. The Ni(I/II)(SCys)2 and Fe(II)(CN)2CO sites are represented with (RC5H4)Ni(I/II) and Fe(II)(diphos)(CO) modules, where diphos = 1,2-C2H4(PPh2)2(dppe) or cis-1,2-C2H2(PPh2)2(dppv). The two bridging thiolate ligands are represented by CH2(CH2S)2(2-) (pdt(2-)), Me2C(CH2S)2(2-) (Me2pdt(2-)), and (C6H5S)2(2-). The reaction of Fe(pdt)(CO)2(dppe) and [(C5H5)3Ni2]BF4 affords [(C5H5)Ni(pdt)Fe(dppe)(CO)]BF4 ([1a]BF4). Monocarbonyl [1a]BF4 features an S = 0 Ni(II)Fe(II) center with five-coordinated iron, as proposed for the Ni-SIa state of the enzyme. One-electron reduction of [1a](+) affords the S = 1/2 derivative [1a](0), which, according to density functional theory (DFT) calculations and electron paramagnetic resonance and Mössbauer spectroscopies, is best described as a Ni(I)Fe(II) compound. The Ni(I)Fe(II) assignment matches that for the Ni-L state in [NiFe]-hydrogenase, unlike recently reported Ni(II)Fe(I)-based models. Compound [1a](0) reacts with strong acids to liberate 0.5 equiv of H2 and regenerate [1a](+), indicating that H2 evolution is catalyzed by [1a](0). DFT calculations were used to investigate the pathway for H2 evolution and revealed that the mechanism can proceed through two isomers of [1a](0) that differ in the stereochemistry of the Fe(dppe)CO center. Calculations suggest that protonation of [1a](0) (both isomers) affords Ni(III)-H-Fe(II) intermediates, which represent mimics of the Ni-C state of the enzyme.

  9. Evolution of Microstructure and Texture During Hot Compression of a Ni-Fe-Cr Superalloy

    NASA Astrophysics Data System (ADS)

    Coryell, S. P.; Findley, K. O.; Mataya, M. C.; Brown, E.

    2012-02-01

    Superalloys are being employed in more extreme conditions requiring higher strength, which requires producers to forge products to finer grain sizes with less grain size variability. To assess grain size, crystallographic texture, and substructure as a function of forging conditions, frictionless uniaxial compression testing characteristic of hot working was performed on INCOLOY 945 (Special Metals Corporation, Huntington, WV), which is a newly developed hybrid of alloys 718 and 925, over a range of temperatures and strain rates. The microstructure and texture were investigated comprehensively using light optical microscopy, electron backscatter diffraction (EBSD), electron channeling contrast imaging (ECCI), and transmission electron microscopy (TEM) to provide detailed insight into microstructure evolution mechanisms. Dynamic recrystallization, nucleated by grain/twin boundary bulging with occasional subgrain rotation, was found to be a dominant mechanism for grain refinement in INCOLOY 945. At higher strain rates, static recrystallization occurred by grain boundary migration. During deformation, duplex slip along {111} planes occurred until a stable <110> fiber compression texture was established. Recrystallization textures were mostly random but shifted toward the compression texture with subsequent deformation. An exception occurred at 1423 K (1150 °C) and 0.001 seconds-1, the condition with the largest fraction of recrystallized grains, where a <100> fiber texture developed, which may be indicative of preferential growth of specific grain orientations.

  10. Structure, magnetic ordering, and spin filtering efficiency of NiFe{sub 2}O{sub 4}(111) ultrathin films

    SciTech Connect

    Matzen, S.; Moussy, J.-B.; Wei, P.; Gatel, C.; Cezar, J. C.; Arrio, M. A.; Sainctavit, Ph.; Moodera, J. S.

    2014-05-05

    NiFe{sub 2}O{sub 4}(111) ultrathin films (3–5 nm) have been grown by oxygen-assisted molecular beam epitaxy and integrated as effective spin-filter barriers. Structural and magnetic characterizations have been performed in order to investigate the presence of defects that could limit the spin filtering efficiency. These analyses have revealed the full strain relaxation of the layers with a cationic order in agreement with the inverse spinel structure but also the presence of antiphase boundaries. A spin-polarization up to +25% has been directly measured by the Meservey-Tedrow technique in Pt(111)/NiFe{sub 2}O{sub 4}(111)/γ-Al{sub 2}O{sub 3}(111)/Al tunnel junctions. The unexpected positive sign and relatively small value of the spin-polarization are discussed, in comparison with predictions and previous indirect tunnelling magnetoresistance measurements.

  11. Multiwall carbon nanotubes decorated with NiFe2O4 magnetic nanoparticles, a new catalyst for voltammetric determination of cefixime.

    PubMed

    Ensafi, Ali A; Allafchian, Ali R

    2013-02-01

    Multiwall carbon nanotubes were decorated with synthesized NiFe(2)O(4) magnetic nanoparticles. The new materials were characterized with different techniques such as transform infrared spectroscopy, transmission electron microscopy, atomic force microscopy and electrochemical impedance spectroscopy. The multiwall carbon nanotubes decorated with NiFe(2)O(4) magnetic nanoparticles was used as a new mediator for the voltammetric determination of cefixime. Under the optimum conditions at pH 8.0, the oxidation of cefixime was occurred at 850 mV at the surface of the modified electrode. Linear sweep voltammetry exhibited two wide linear dynamic ranges of 0.1-100 and 100-600 μmol L(-1) cefixime. The detection limit was found to be 0.02 μmol L(-1) cefixime. Finally, the modified electrode showed good sensitivity, selectivity and stability for the determination of cefixime in real samples.

  12. In-situ synthesis of magnetic (NiFe{sub 2}O{sub 4}/CuO/FeO) nanocomposites

    SciTech Connect

    Srivastava, Manish; Ojha, Animesh K.; Chaubey, S.; Singh, Jay

    2010-11-15

    In-situ synthesis of magnetic nanocomposites with (NiFe{sub 2}O{sub 4}/CuO/FeO) crystal phases has been done using a sol-gel method by taking a non-stoichiometric composition of the precursors. The average particle size of the nanocomposites was calculated using X-ray diffraction (XRD) and high resolution tunneling electron microscope (HR-TEM) and it turns out to be {approx}20 nm. The vibrating sample magnetometer (VSM) measurements demonstrate the ferromagnetic nature of the nanocomposites. The synthesized nanocomposite was used to prepare magnetic fluid using tetramethylammonium hydroxide as a surfactant and its stability in the solution was also discussed. -- Graphical abstract: Magnetic nanocomposites containing (NiFe{sub 2}O{sub 4}/CuO/FeO) phases having particle size {approx}17 nm were synthesized by a sol-gel method. The synthesized nanocomposites exhibit ferromagnetic nature with small value of coercivity.

  13. Deletion of a gene cluster for [Ni-Fe] hydrogenase maturation in the anaerobic hyperthermophilic bacterium Caldicellulosiruptor bescii identifies its role in hydrogen metabolism.

    PubMed

    Cha, Minseok; Chung, Daehwan; Westpheling, Janet

    2016-02-01

    The anaerobic, hyperthermophlic, cellulolytic bacterium Caldicellulosiruptor bescii grows optimally at ∼80 °C and effectively degrades plant biomass without conventional pretreatment. It utilizes a variety of carbohydrate carbon sources, including both C5 and C6 sugars, released from plant biomass and produces lactate, acetate, CO2, and H2 as primary fermentation products. The C. bescii genome encodes two hydrogenases, a bifurcating [Fe-Fe] hydrogenase and a [Ni-Fe] hydrogenase. The [Ni-Fe] hydrogenase is the most widely distributed in nature and is predicted to catalyze hydrogen production and to pump protons across the cellular membrane creating proton motive force. Hydrogenases are the key enzymes in hydrogen metabolism and their crystal structure reveals complexity in the organization of their prosthetic groups suggesting extensive maturation of the primary protein. Here, we report the deletion of a cluster of genes, hypABFCDE, required for maturation of the [Ni-Fe] hydrogenase. These proteins are specific for the hydrogenases they modify and are required for hydrogenase activity. The deletion strain grew more slowly than the wild type or the parent strain and produced slightly less hydrogen overall, but more hydrogen per mole of cellobiose. Acetate yield per mole of cellobiose was increased ∼67 % and ethanol yield per mole of cellobiose was decreased ∼39 %. These data suggest that the primary role of the [Ni-Fe] hydrogenase is to generate a proton gradient in the membrane driving ATP synthesis and is not the primary enzyme for hydrogen catalysis. In its absence, ATP is generated from increased acetate production resulting in more hydrogen produced per mole of cellobiose.

  14. The bidirectional NiFe-hydrogenase in Synechocystis sp. PCC 6803 is reduced by flavodoxin and ferredoxin and is essential under mixotrophic, nitrate-limiting conditions.

    PubMed

    Gutekunst, Kirstin; Chen, Xi; Schreiber, Karoline; Kaspar, Ursula; Makam, Srinivas; Appel, Jens

    2014-01-24

    Cyanobacteria are able to use solar energy for the production of hydrogen. It is generally accepted that cyanobacterial NiFe-hydrogenases are reduced by NAD(P)H. This is in conflict with thermodynamic considerations, as the midpoint potentials of NAD(P)H do not suffice to support the measured hydrogen production under physiological conditions. We show that flavodoxin and ferredoxin directly reduce the bidirectional NiFe-hydrogenase of Synechocystis sp. PCC 6803 in vitro. A merodiploid ferredoxin-NADP reductase mutant produced correspondingly more photohydrogen. We furthermore found that the hydrogenase receives its electrons via pyruvate:flavodoxin/ferredoxin oxidoreductase (PFOR)-flavodoxin/ferredoxin under fermentative conditions, enabling the cells to gain ATP. These results strongly support that the bidirectional NiFe-hydrogenases in cyanobacteria function as electron sinks for low potential electrons from photosystem I and as a redox balancing device under fermentative conditions. However, the selective advantage of this enzyme is not known. No strong phenotype of mutants lacking the hydrogenase has been found. Because bidirectional hydrogenases are widespread in aquatic nutrient-rich environments that are capable of triggering phytoplankton blooms, we mimicked those conditions by growing cells in the presence of increased amounts of dissolved organic carbon and dissolved organic nitrogen. Under these conditions the hydrogenase was found to be essential. As these conditions close the two most important sinks for reduced flavodoxin/ferredoxin (CO2-fixation and nitrate reduction), this discovery further substantiates the connection between flavodoxin/ferredoxin and the NiFe-hydrogenase. PMID:24311779

  15. Impact of the iron-sulfur cluster proximal to the active site on the catalytic function of an O2-tolerant NAD(+)-reducing [NiFe]-hydrogenase.

    PubMed

    Karstens, Katja; Wahlefeld, Stefan; Horch, Marius; Grunzel, Miriam; Lauterbach, Lars; Lendzian, Friedhelm; Zebger, Ingo; Lenz, Oliver

    2015-01-20

    The soluble NAD(+)-reducing hydrogenase (SH) from Ralstonia eutropha H16 belongs to the O2-tolerant subtype of pyridine nucleotide-dependent [NiFe]-hydrogenases. To identify molecular determinants for the O2 tolerance of this enzyme, we introduced single amino acids exchanges in the SH small hydrogenase subunit. The resulting mutant strains and proteins were investigated with respect to their physiological, biochemical, and spectroscopic properties. Replacement of the four invariant conserved cysteine residues, Cys41, Cys44, Cys113, and Cys179, led to unstable protein, strongly supporting their involvement in the coordination of the iron-sulfur cluster proximal to the catalytic [NiFe] center. The Cys41Ser exchange, however, resulted in an SH variant that displayed up to 10% of wild-type activity, suggesting that the coordinating role of Cys41 might be partly substituted by the nearby Cys39 residue, which is present only in O2-tolerant pyridine nucleotide-dependent [NiFe]-hydrogenases. Indeed, SH variants carrying glycine, alanine, or serine in place of Cys39 showed increased O2 sensitivity compared to that of the wild-type enzyme. Substitution of further amino acids typical for O2-tolerant SH representatives did not greatly affect the H2-oxidizing activity in the presence of O2. Remarkably, all mutant enzymes investigated by electron paramagnetic resonance spectroscopy did not reveal significant spectral changes in relation to wild-type SH, showing that the proximal iron-sulfur cluster does not contribute to the wild-type spectrum. Interestingly, exchange of Trp42 by serine resulted in a completely redox-inactive [NiFe] site, as revealed by infrared spectroscopy and H2/D(+) exchange experiments. The possible role of this residue in electron and/or proton transfer is discussed.

  16. The influence of oxygen on [NiFe]-hydrogenase cofactor biosynthesis and how ligation of carbon monoxide precedes cyanation.

    PubMed

    Stripp, Sven T; Lindenstrauss, Ute; Granich, Claudia; Sawers, R Gary; Soboh, Basem

    2014-01-01

    The class of [NiFe]-hydrogenases is characterized by a bimetallic cofactor comprising low-spin nickel and iron ions, the latter of which is modified with a single carbon monoxide (CO) and two cyanide (CN-) molecules. Generation of these ligands in vivo requires a complex maturation apparatus in which the HypC-HypD complex acts as a 'construction site' for the Fe-(CN)2CO portion of the cofactor. The order of addition of the CO and CN- ligands determines the ultimate structure and catalytic efficiency of the cofactor; however much debate surrounds the succession of events. Here, we present an FT-IR spectroscopic analysis of HypC-HypD isolated from a hydrogenase-competent wild-type strain of Escherichia coli. In contrast to previously reported samples, HypC-HypD showed spectral contributions indicative of an electron-rich Fe-CO cofactor, at the same time lacking any Fe-CN- signatures. This immature iron site binds external CO and undergoes oxidative damage when in contact with O2. Binding of CO protects the site against loss of spectral features associated with O2 damage. Our findings strongly suggest that CO ligation precedes cyanation in vivo. Furthermore, the results provide a rationale for the deleterious effects of O2 on in vivo cofactor biosynthesis.

  17. A threonine stabilizes the NiC and NiR catalytic intermediates of [NiFe]-hydrogenase.

    PubMed

    Abou-Hamdan, Abbas; Ceccaldi, Pierre; Lebrette, Hugo; Gutiérrez-Sanz, Oscar; Richaud, Pierre; Cournac, Laurent; Guigliarelli, Bruno; De Lacey, Antonio L; Léger, Christophe; Volbeda, Anne; Burlat, Bénédicte; Dementin, Sébastien

    2015-03-27

    The heterodimeric [NiFe] hydrogenase from Desulfovibrio fructosovorans catalyzes the reversible oxidation of H2 into protons and electrons. The catalytic intermediates have been attributed to forms of the active site (NiSI, NiR, and NiC) detected using spectroscopic methods under potentiometric but non-catalytic conditions. Here, we produced variants by replacing the conserved Thr-18 residue in the small subunit with Ser, Val, Gln, Gly, or Asp, and we analyzed the effects of these mutations on the kinetic (H2 oxidation, H2 production, and H/D exchange), spectroscopic (IR, EPR), and structural properties of the enzyme. The mutations disrupt the H-bond network in the crystals and have a strong effect on H2 oxidation and H2 production turnover rates. However, the absence of correlation between activity and rate of H/D exchange in the series of variants suggests that the alcoholic group of Thr-18 is not necessarily a proton relay. Instead, the correlation between H2 oxidation and production activity and the detection of the NiC species in reduced samples confirms that NiC is a catalytic intermediate and suggests that Thr-18 is important to stabilize the local protein structure of the active site ensuring fast NiSI-NiC-NiR interconversions during H2 oxidation/production.

  18. The mechanism of hydrogen uptake in [NiFe] hydrogenase: first-principles molecular dynamics investigation of a model compound.

    PubMed

    Furlan, Sara; La Penna, Giovanni

    2012-01-01

    The recent discovery of a model compounds of [NiFe] hydrogenase that catalyzes the heterolytic cleavage of the H(2) molecule into a proton and a stable hydride in water solution under room conditions opened up the possibility to understand the mechanism of H(2) uptake by this peculiar class of enzymes. The simplest model compound belongs to the class of NiRu bimetallic cationic complexes mimicking, in water solution and at room conditions, the hydrogenase active site. By using first-principles molecular dynamics computer simulations, in the Car-Parrinello scheme, we investigated models including the water solvent and nitrate counterions. Several simulations, starting from different initial configurations, provided information on the first step of the H(2) cleavage: (1) the pathway of H(2) approach towards the active site; (2) the role of the ruthenium-bonded water molecule in providing a base that extracts the proton from the activated H(2) molecule; (3) the minor role of Ni in activating the H(2) molecule and its role in stabilizing the hydride produced. PMID:21892688

  19. The Influence of Oxygen on [NiFe]–Hydrogenase Cofactor Biosynthesis and How Ligation of Carbon Monoxide Precedes Cyanation

    PubMed Central

    Stripp, Sven T.; Lindenstrauss, Ute; Granich, Claudia; Sawers, R. Gary; Soboh, Basem

    2014-01-01

    The class of [NiFe]–hydrogenases is characterized by a bimetallic cofactor comprising low–spin nickel and iron ions, the latter of which is modified with a single carbon monoxide (CO) and two cyanide (CN−) molecules. Generation of these ligands in vivo requires a complex maturation apparatus in which the HypC–HypD complex acts as a ‘construction site’ for the Fe–(CN)2CO portion of the cofactor. The order of addition of the CO and CN– ligands determines the ultimate structure and catalytic efficiency of the cofactor; however much debate surrounds the succession of events. Here, we present an FT–IR spectroscopic analysis of HypC–HypD isolated from a hydrogenase–competent wild–type strain of Escherichia coli. In contrast to previously reported samples, HypC–HypD showed spectral contributions indicative of an electron–rich Fe–CO cofactor, at the same time lacking any Fe–CN– signatures. This immature iron site binds external CO and undergoes oxidative damage when in contact with O2. Binding of CO protects the site against loss of spectral features associated with O2 damage. Our findings strongly suggest that CO ligation precedes cyanation in vivo. Furthermore, the results provide a rationale for the deleterious effects of O2 on in vivo cofactor biosynthesis. PMID:25211029

  20. Protonation states of intermediates in the reaction mechanism of [NiFe] hydrogenase studied by computational methods.

    PubMed

    Dong, Geng; Ryde, Ulf

    2016-06-01

    The [NiFe] hydrogenases catalyse the reversible conversion of H2 to protons and electrons. The active site consists of a Fe ion with one carbon monoxide, two cyanide, and two cysteine (Cys) ligands. The latter two bridge to a Ni ion, which has two additional terminal Cys ligands. It has been suggested that one of the Cys residues is protonated during the reaction mechanism. We have used combined quantum mechanical and molecular mechanics (QM/MM) geometry optimisations, large QM calculations with 817 atoms, and QM/MM free energy simulations, using the TPSS and B3LYP methods with basis sets extrapolated to the quadruple zeta level to determine which of the four Cys residues is more favourable to protonate for four putative states in the reaction mechanism, Ni-SIa, Ni-R, Ni-C, and Ni-L. The calculations show that for all states, the terminal Cys-546 residue is most easily protonated by 14-51 kJ/mol, owing to a more favourable hydrogen-bond pattern around this residue in the protein. PMID:26940957

  1. Proton Inventory and Dynamics in the Nia-S to Nia-C Transition of a [NiFe] Hydrogenase.

    PubMed

    Greene, Brandon L; Wu, Chang-Hao; Vansuch, Gregory E; Adams, Michael W W; Dyer, R Brian

    2016-03-29

    Hydrogenases (H2ases) represent one of the most striking examples of biological proton-coupled electron transfer (PCET) chemistry, functioning in facile proton reduction and H2 oxidation involving long-range proton and electron transport. Spectroscopic and electrochemical studies of the [NiFe] H2ases have identified several catalytic intermediates, but the details of their interconversion are still a matter of debate. Here we use steady state and time-resolved infrared spectroscopy, sensitive to the CO ligand of the active site iron, as a probe of the proton inventory as well as electron and proton transfer dynamics in the soluble hydrogenase I from Pyrococcus furiosus. Subtle shifts in infrared signatures associated with the Nia-C and Nia-S states as a function of pH revealed an acid-base equilibrium associated with an ionizable amino acid near the active site. Protonation of this residue was found to correlate with the photoproduct distribution that results from hydride photolysis of the Nia-C state, in which one of the two photoproduct states becomes inaccessible at low pH. Additionally, the ability to generate Nia-S via PCET from Nia-C was weakened at low pH, suggesting prior protonation of the proton acceptor. Kinetic and thermodynamic analysis of electron and proton transfer with respect to the various proton inventories was utilized to develop a chemical model for reversible hydride oxidation involving two intermediates differing in their hydrogen bonding character.

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

    PubMed

    Evans, Rhiannon M; Armstrong, Fraser A

    2014-01-01

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

  3. Tunneling behavior in ion-assist ion-beam sputtered CoFe/MgO/NiFe magnetic tunnel junctions

    SciTech Connect

    Singh, Braj Bhusan; Chaudhary, Sujeet; Pandya, Dinesh K.

    2012-11-15

    Graphical abstract: Display Omitted Highlights: ► Dual ion beam sputtered MgO barrier for MTJs. ► ∼12% TMR at 60 K. ► Glazman and Matveev model fitted for quantification of elastic and inelastic tunneling conductance through barrier. -- Abstract: Magnetic tunnel junctions (MTJs) consisting of CoFe and NiFe as ferromagnetic electrodes and MgO as insulating barrier fabricated through in situ shadow masking employing ion beam sputtering are studied for their tunneling magnetoresistance (TMR) and temperature dependence of the tunneling conductance behavior. The tunneling characteristics of these MTJs exhibited barrier height of 0.7 eV and width of 3.3 nm. These MTJs possessed ∼12% TMR at 60 K. The temperature dependence of conductance behavior of these junctions have revealed finite contributions from inelastic tunneling through the barrier via hopping conduction via present localized states which arise due to the presence of ionic interstitial defects in the MgO oxide barrier. The fitting of the data reveals that thirteenth order of hopping conduction is operative through MgO barrier.

  4. Thermal relaxation and collective dynamics of interacting aerosol-generated hexagonal NiFe2O4 nanoparticles.

    PubMed

    Ortega, D; Kuznetsov, M V; Morozov, Yu G; Belousova, O V; Parkin, I P

    2013-12-28

    This article reports on the magnetic properties of interacting uncoated nickel ferrite (NiFe2O4) nanoparticles synthesized through an aerosol levitation-jet technique. A comprehensive set of samples with different compositions of background gas and metal precursors, as well as applied electric field intensities, has been studied. Nanoparticles prepared under a field of 210 kV m(-1) show moderately high-field irreversibility and shifted hysteresis loops after field-cooling, also exhibiting a joint temperature decrease of the exchange field and coercivity. The appearance of memory effects has been checked using the genuine ZFC protocol and the observed behavior cannot be fully explained in terms of thermal relaxation. Although dipolar interactions prevail, exchange interactions occur to a certain extent within a narrow range of applied fields. The origin of the slow dynamics in the system is found to be given by the interplay of the distribution of energy barriers due to size dispersion and the cooperative dynamics associated with frustrated interactions. PMID:24196451

  5. Magnetic properties of La-substituted NiFe 2O 4 via egg-white precursor route

    NASA Astrophysics Data System (ADS)

    Al Angari, Y. M.

    2011-07-01

    Nano-sized NiFe 2- xLa xO 4 ferrites ( x=0.00, 0.01, 0.02, 0.03, 0.04, 0.5, 0.07 and 0.09) were synthesized for the first time by using metal nitrate and egg-white extract in aqueous medium. The ferrites were characterized by DTA-TG, XRD, TEM, FT-IR and VSM techniques. The thermal decomposition behavior revealed that the precursors were completely decomposed at about 420 °C. TEM image shows agglomerated nanoparticles with crystallite sizes agrees well with that estimated by XRD measurement. XRD patterns show a secondary phase of LaFeO 3 besides the cubic structure of the La-substituted ferrites. The lattice parameters, X-ray density and crystallite size were found to increase with the increasing La content. The VSM measurement exhibited a ferromagnetic property for all the samples at room temperature. With increasing La, Ms was found to decrease while Hc increased. The decrease in the saturation magnetization is attributed to the paramagnetic properties of lanthanum, which prefer to substitute iron present in the octahedral sites. The increase in the coercivity is due to either the stronger magnetocrystalline anisotropy induced by La substitution or the change in the crystallite size.

  6. Effects of particle composition and environmental parameters on catalytic hydrodechlorination of trichloroethylene by nanoscale bimetallic Ni-Fe.

    PubMed

    Wei, Jianjun; Qian, Yajing; Liu, Wenjuan; Wang, Lutao; Ge, Yijie; Zhang, Jianghao; Yu, Jiang; Ma, Xingmao

    2014-05-01

    Catalytic nickel was successfully incorporated into nanoscale iron to enhance its dechlorination efficiency for trichloroethylene (TCE), one of the most commonly detected chlorinated organic compounds in groundwater. Ethane was the predominant product. The greatest dechlorination efficiency was achieved at 22 molar percent of nickel. This nanoscale Ni-Fe is poorly ordered and inhomogeneous; iron dissolution occurred whereas nickel was relatively stable during the 24-hr reaction. The morphological characterization provided significant new insights on the mechanism of catalytic hydrodechlorination by bimetallic nanoparticles. TCE degradation and ethane production rates were greatly affected by environmental parameters such as solution pH, temperature and common groundwater ions. Both rate constants decreased and then increased over the pH range of 6.5 to 8.0, with the minimum value occurring at pH 7.5. TCE degradation rate constant showed an increasing trend over the temperature range of 10 to 25°C. However, ethane production rate constant increased and then decreased over the range, with the maximum value occurring at 20°C. Most salts in the solution appeared to enhance the reaction in the first half hour but overall they displayed an inhibitory effect. Combined ions showed a similar effect as individual salts. PMID:25079647

  7. Relation between anaerobic inactivation and oxygen tolerance in a large series of NiFe hydrogenase mutants

    PubMed Central

    Abou Hamdan, Abbas; Liebgott, Pierre-Pol; Fourmond, Vincent; Gutiérrez-Sanz, Oscar; De Lacey, Antonio L.; Infossi, Pascale; Rousset, Marc; Dementin, Sébastien; Léger, Christophe

    2012-01-01

    Nickel-containing hydrogenases, the biological catalysts of oxidation and production, reversibly inactivate under anaerobic, oxidizing conditions. We aim at understanding the mechanism of (in)activation and what determines its kinetics, because there is a correlation between fast reductive reactivation and oxygen tolerance, a property of some hydrogenases that is very desirable from the point of view of biotechnology. Direct electrochemistry is potentially very useful for learning about the redox-dependent conversions between active and inactive forms of hydrogenase, but the voltammetric signals are complex and often misread. Here we describe simple analytical models that we used to characterize and compare 16 mutants, obtained by substituting the position-74 valine of the -sensitive NiFe hydrogenase from Desulfovibrio fructosovorans. We observed that this substitution can accelerate reactivation up to 1,000-fold, depending on the polarity of the position 74 amino acid side chain. In terms of kinetics of anaerobic (in)activation and oxygen tolerance, the valine-to-histidine mutation has the most spectacular effect: The V74H mutant compares favorably with the -tolerant hydrogenase from Aquifex aeolicus, which we use here as a benchmark. PMID:23169623

  8. A Threonine Stabilizes the NiC and NiR Catalytic Intermediates of [NiFe]-hydrogenase*

    PubMed Central

    Abou-Hamdan, Abbas; Ceccaldi, Pierre; Lebrette, Hugo; Gutiérrez-Sanz, Oscar; Richaud, Pierre; Cournac, Laurent; Guigliarelli, Bruno; De Lacey, Antonio L.; Léger, Christophe; Volbeda, Anne; Burlat, Bénédicte; Dementin, Sébastien

    2015-01-01

    The heterodimeric [NiFe] hydrogenase from Desulfovibrio fructosovorans catalyzes the reversible oxidation of H2 into protons and electrons. The catalytic intermediates have been attributed to forms of the active site (NiSI, NiR, and NiC) detected using spectroscopic methods under potentiometric but non-catalytic conditions. Here, we produced variants by replacing the conserved Thr-18 residue in the small subunit with Ser, Val, Gln, Gly, or Asp, and we analyzed the effects of these mutations on the kinetic (H2 oxidation, H2 production, and H/D exchange), spectroscopic (IR, EPR), and structural properties of the enzyme. The mutations disrupt the H-bond network in the crystals and have a strong effect on H2 oxidation and H2 production turnover rates. However, the absence of correlation between activity and rate of H/D exchange in the series of variants suggests that the alcoholic group of Thr-18 is not necessarily a proton relay. Instead, the correlation between H2 oxidation and production activity and the detection of the NiC species in reduced samples confirms that NiC is a catalytic intermediate and suggests that Thr-18 is important to stabilize the local protein structure of the active site ensuring fast NiSI-NiC-NiR interconversions during H2 oxidation/production. PMID:25666617

  9. Structural and electrical properties of Cu doped NiFe2O4 nanoparticles prepared through modified citrate gel method

    NASA Astrophysics Data System (ADS)

    Batoo, Khalid Mujasam

    2011-12-01

    Nanoparticles of polycrystalline NiFe2-xCuxO4 (0.0≤x≤0.05) ferrites were prepared through the modified citrate-gel method. The samples were obtained as dried gel after the successful chemical reaction of their respective metal nitrate solutions in the midst of citric acid as catalyst. X-ray diffraction (XRD) and selective area electron diffraction (SAED) confirmed the single phase nature of all the samples with an average particle size of 19.8 (±1). Fourier transformation infrared spectroscopy (FTIR) shows the presence of two broad vibrational bands between 400 and 1000 cm-1 corresponding to the tetrahedral and the octahedral sites. The variation of dielectric properties (ɛ‧, ɛ″, tan δ) and ac conductivity (σac), with frequency reveals that the dispersion is due to the Maxwell-Wagner type of interfacial polarization in general and due to hopping of charges between Fe+2 and Fe+3 as well as between Ni+2 and Ni+3 ions at B-sites. The complex impedance spectroscopy has been used to study the effect of grain and grain boundary on the electrical properties of all the ferrite nanoparticles.

  10. Relation between anaerobic inactivation and oxygen tolerance in a large series of NiFe hydrogenase mutants.

    PubMed

    Abou Hamdan, Abbas; Liebgott, Pierre-Pol; Fourmond, Vincent; Gutiérrez-Sanz, Oscar; De Lacey, Antonio L; Infossi, Pascale; Rousset, Marc; Dementin, Sébastien; Léger, Christophe

    2012-12-01

    Nickel-containing hydrogenases, the biological catalysts of oxidation and production, reversibly inactivate under anaerobic, oxidizing conditions. We aim at understanding the mechanism of (in)activation and what determines its kinetics, because there is a correlation between fast reductive reactivation and oxygen tolerance, a property of some hydrogenases that is very desirable from the point of view of biotechnology. Direct electrochemistry is potentially very useful for learning about the redox-dependent conversions between active and inactive forms of hydrogenase, but the voltammetric signals are complex and often misread. Here we describe simple analytical models that we used to characterize and compare 16 mutants, obtained by substituting the position-74 valine of the -sensitive NiFe hydrogenase from Desulfovibrio fructosovorans. We observed that this substitution can accelerate reactivation up to 1,000-fold, depending on the polarity of the position 74 amino acid side chain. In terms of kinetics of anaerobic (in)activation and oxygen tolerance, the valine-to-histidine mutation has the most spectacular effect: The V74H mutant compares favorably with the -tolerant hydrogenase from Aquifex aeolicus, which we use here as a benchmark. PMID:23169623

  11. Magnetization reversal in Ni/FeF2 heterostructures with the coexistence of positive and negative exchange bias

    NASA Astrophysics Data System (ADS)

    Kovylina, Miroslavna; Morales, Rafael; Labarta, Amílcar; Batlle, Xavier

    2012-12-01

    Magnetization reversal mechanisms are studied in Ni/FeF2 heterostructures with the coexistence of positive and negative exchanged bias (PEB/NEB), showing single and double hysteresis loops (DHL) in magnetoresistance measurements. Micromagnetic simulations show that PEB and NEB domains of a minimum critical size must be introduced in order to reproduce the occurrence of DHLs. The simulations reveal that different magnetic configurations and, hence, different magnetization reversal processes take place in a ferromagnet (FM) on top of minority PEB domains that are either greater or smaller than the critical size. In particular, for the case of DHLs, core reversal of a depthwise domain wall is observed over minority PEB domains when the magnetic field is decreased from positive saturation. As the field is further decreased, a complex domain-wall evolution takes place in the FM, including the dependences of the domain-wall width and domain size on the magnetic field and distance from the antiferromagnet (AF). These effects should be taken into account when the domain size is estimated from data measured by depth-dependent techniques since they average the distribution of domain sizes in the FM for different distances from the AF.

  12. O2-stable membrane-bound [NiFe]hydrogenase from a newly isolated Citrobacter sp. S-77.

    PubMed

    Eguchi, Shigenobu; Yoon, Ki-Seok; Ogo, Seiji

    2012-11-01

    Hydrogenases are of great interest due to their potential use in H(2)-based technology. However, most hydrogenases are highly sensitive to O(2), which have been the major bottleneck in hydrogenase studies. Here we report an O(2)-stable membrane-bound [NiFe]hydrogenase (MBH) purified from a newly isolated strain, S-77. According to the 16S rRNA gene sequence and phylogenetic analysis of the strain S-77, it belongs to the genus of Citrobacter. In vitro experiments using the cytoplasmic membrane of strain S-77 suggested that a cytochrome b acts as the physiological electron acceptor of the MBH. The purified MBH was composed of a dimer of heterodimers, consisting of two distinct subunits with the molecular weights of 58.5 and 38.5 kDa. The enzyme showed a specific activity for H(2)-oxidation of 661 U/mg, which is 35-fold greater than that for H(2)-production of 18.7 U/mg. Notably, the MBH showed a remarkable O(2)-stability, maintaining almost 95% of its original activity even after incubation for 30 h in air at 4°C. These results suggest that the O(2)-stable MBH may play an important role in the H(2)-metabolic pathway under the aerobic conditions of Citrobacter sp. S-77. This is the first report of the purification and biochemical characterization of an O(2)-stable MBH from the genus of Citrobacter.

  13. EFFECT OF ANNEALING TEMPERATURE ON THE STRUCTURE AND AC MAGNETIC PROPERTIES OF Fe73Cu1Nb3.5-xVxSi13.5B9 (x = 1.0, 1.5, 2.0) NANOCRYSTALLINE SOFT MAGNETIC ALLOYS

    NASA Astrophysics Data System (ADS)

    Lu, Wei; Huang, Ping; Wang, Yuxin; Yan, Biao

    2013-07-01

    In this paper, Nb element was partially replaced by V element in Finemet-type Fe73Cu1Nb3.5-xVxSi13.5B9 (x = 1, 1.5, 2) alloys and the effect of annealing temperatures on the microstructure and AC magnetic properties of the samples are studied. The annealing temperatures affect the grain sizes of the bcc α-Fe phase greatly. When the annealing temperature is between 540-560°C, the samples have better AC magnetic properties than the samples annealed at other temperatures. The optimized annealing temperature of the studied samples is around 560°C. The coercivity and iron loss of the V2 sample is a little bit higher than that of V1 and V1.5 alloys while the amplitude permeability of V2 alloy is larger than that of V1 and V1.5, which indicate that the content of V element has strong influence on the magnetic properties of nanocrystalline soft magnetic alloys.

  14. Nanocrystalline nanowires: I. Structure.

    PubMed

    Allen, Philip B

    2007-01-01

    Geometric constructions of possible atomic arrangements are suggested for inorganic nanowires. These are fragments of bulk crystals, and can be called "nanocrystalline" nanowires (NCNW). To minimize surface polarity, nearly one-dimensional formula units, oriented along the growth axis, generate NCNWs by translation and rotation.

  15. Nanocrystalline heterojunction materials

    SciTech Connect

    Elder, Scott H.; Su, Yali; Gao, Yufei; Heald, Steve M.

    2003-07-15

    Mesoporous nanocrystalline titanium dioxide heterojunction materials are disclosed. In one disclosed embodiment, materials comprising a core of titanium dioxide and a shell of a molybdenum oxide exhibit a decrease in their photoadsorption energy as the size of the titanium dioxide core decreases.

  16. Nanocrystalline Heterojunction Materials

    SciTech Connect

    Elder, Scott H.; Su, Yali; Gao, Yufei; Heald, Steve M.

    2004-02-03

    Mesoporous nanocrystalline titanium dioxide heterojunction materials and methods of making the same are disclosed. In one disclosed embodiment, materials comprising a core of titanium dioxide and a shell of a molybdenum oxide exhibit a decrease in their photoadsorption energy as the size of the titanium dioxide core decreases.

  17. Elastic and hierarchical porous carbon nanofibrous membranes incorporated with NiFe2O4 nanocrystals for highly efficient capacitive energy storage.

    PubMed

    Ge, Jianlong; Fan, Gang; Si, Yang; He, Jianxin; Kim, Hak-Yong; Ding, Bin; Al-Deyab, Salem S; El-Newehy, Mohamed; Yu, Jianyong

    2016-01-28

    Flexible membranes created from porous carbon nanofibers (CNFs) hold great promise in the next generation wearable energy storage devices, but challenges still remain due to the poor mechanical properties of porous carbon nanofibers. Here, we report a facile strategy to fabricate elastic and hierarchical porous CNF membranes with NiFe2O4 nanocrystals embedded via multicomponent electrospinning and nano-doping methods. Benefiting from the scattering effect of NiFe2O4 nanocrystals and graphitized carbon layers for the condensed stress, the resultant CNF membranes exhibit an enhanced elasticity with a bending radius <12 μm, rapid recovery from the deformations, and a superior softness. Quantitative pore size distribution and fractal analysis reveal that the CNFs possessed tunable porous structures with a high surface area of 493 m(2) g(-1) and a pore volume of 0.31 cm(3) g(-1). Benefiting from the robust mechanical stability, hierarchical porous structures and good electrochemical properties, the NiFe2O4 doped CNF membranes demonstrate a high electrical capacitance of 343 F g(-1), and good reversibility with a cycling efficiency of 97.4% even after 10,000 cycles. The successful synthesis of elastic porous CNF membranes also provided a versatile platform for the design and development of functional CNF based materials for various applications.

  18. Self-assembly formation of hollow Ni-Fe-O nanocage architectures by metal-organic frameworks with high-performance lithium storage

    PubMed Central

    Guo, Hong; Li, Tingting; Chen, Weiwei; Liu, Lixiang; Qiao, Jinli; Zhang, Jiujun

    2015-01-01

    A hollow hybrid Ni-Fe-O nanomaterial (NiFe2O4) is synthesized using a precursor of metal-organic frameworks through a simple and cost-effective method. The unique hollow nanocage structures shorten the length of Li-ion diffusion. The hollow structure offers a sufficient void space, which sufficiently alleviates the mechanical stress caused by volume change. Besides, the hybrid elements allow the volume change to take place in a stepwise manner during electrochemical cycle. And thus, the hierarchical hollow NiFe2O4 nanocage electrode exhibits extraordinary electrochemical performance. The stable cyclic performance is obtained for all rates from 1 C to 10 C. Even when the current reaches 10 C, the capacity can also arrive at 652 mAhg−1. Subsequently, a specific capacity of ca. 975 mAhg−1 is recovered when the current rate reduces back to 1 C after 200 cycles. This strategy that derived from NMOFs may shed light on a new route for large-scale synthesis of hollow porous hybrid nanocages for energy storage, environmental remediation and other novel applications. PMID:26347981

  19. Genetic diversity of Desulfovibrio spp. in environmental samples analyzed by denaturing gradient gel electrophoresis of [NiFe] hydrogenase gene fragments.

    PubMed Central

    Wawer, C; Muyzer, G

    1995-01-01

    The genetic diversity of Desulfovibrio species in environmental samples was determined by denaturing gradient gel electrophoresis (DGGE) of PCR-amplified [NiFe] hydrogenase gene fragments. Five different PCR primers were designed after comparative analysis of [NiFe] hydrogenase gene sequences from three Desulfovibrio species. These primers were tested in different combinations on the genomic DNAs of a variety of hydrogenase-containing and hydrogenase-lacking bacteria. One primer pair was found to be specific for Desulfovibrio species only, while the others gave positive results with other bacteria also. By using this specific primer pair, we were able to amplify the [NiFe] hydrogenase genes of DNAs isolated from environmental samples and to detect the presence of Desulfovibrio species in these samples. However, only after DGGE analysis of these PCR products could the number of different Desulfovibrio species within the samples be determined. DGGE analysis of PCR products from different bioreactors demonstrated up to two bands, while at least five distinguishable bands were detected in a microbial mat sample. Because these bands most likely represent as many Desulfovibrio species present in these samples, we conclude that the genetic diversity of Desulfovibrio species in the natural microbial mat is far greater than that in the experimental bioreactors. PMID:7793940

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

    PubMed Central

    Stripp, Sven T.; Lindenstrauss, Ute; Sawers, R. Gary; Soboh, Basem

    2015-01-01

    [NiFe]–hydrogenases catalyze uptake and evolution of H2 in a wide range of microorganisms. The enzyme is characterized by an inorganic nickel/ iron cofactor, the latter of which carries carbon monoxide and cyanide ligands. In vivo generation of these ligands requires a number of auxiliary proteins, the so–called Hyp family. Initially, HypF binds and activates the precursor metabolite carbamoyl phosphate. HypF catalyzes removal of phosphate and transfers the carbamate group to HypE. In an ATP–dependent condensation reaction, the C–terminal cysteinyl residue of HypE is modified to what has been interpreted as thiocyanate. This group is the direct precursor of the cyanide ligands of the [NiFe]–hydrogenase active site cofactor. We present a FT–IR analysis of HypE and HypF as isolated from E. coli. We follow the HypF–catalyzed cyanation of HypE in vitro and screen for the influence of carbamoyl phosphate and ATP. To elucidate on the differences between HypE and the HypEF complex, spectro–electrochemistry was used to map the vibrational Stark effect of naturally cyanated HypE. The IR signature of HypE could ultimately be assigned to isothiocyanate (–N=C=S) rather than thiocyanate (–S–C≡N). This has important implications for cyanyl–group channeling during [NiFe]–hydrogenase cofactor generation. PMID:26186649

  1. Self-assembly formation of hollow Ni-Fe-O nanocage architectures by metal-organic frameworks with high-performance lithium storage

    NASA Astrophysics Data System (ADS)

    Guo, Hong; Li, Tingting; Chen, Weiwei; Liu, Lixiang; Qiao, Jinli; Zhang, Jiujun

    2015-09-01

    A hollow hybrid Ni-Fe-O nanomaterial (NiFe2O4) is synthesized using a precursor of metal-organic frameworks through a simple and cost-effective method. The unique hollow nanocage structures shorten the length of Li-ion diffusion. The hollow structure offers a sufficient void space, which sufficiently alleviates the mechanical stress caused by volume change. Besides, the hybrid elements allow the volume change to take place in a stepwise manner during electrochemical cycle. And thus, the hierarchical hollow NiFe2O4 nanocage electrode exhibits extraordinary electrochemical performance. The stable cyclic performance is obtained for all rates from 1 C to 10 C. Even when the current reaches 10 C, the capacity can also arrive at 652 mAhg-1. Subsequently, a specific capacity of ca. 975 mAhg-1 is recovered when the current rate reduces back to 1 C after 200 cycles. This strategy that derived from NMOFs may shed light on a new route for large-scale synthesis of hollow porous hybrid nanocages for energy storage, environmental remediation and other novel applications.

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

    SciTech Connect

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

    2015-03-14

    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, 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.

  3. In situ studies of surface of NiFe2O4 catalyst during complete oxidation of methane

    SciTech Connect

    Zhang, Shiran; Shan, Junjun; Nie, Longhui; Nguyen, Luan; Wu, Zili; Tao, Franklin

    2015-12-21

    Here, NiFe2O4 with an inverse spinel structure exhibits high activity for a complete oxidation of methane at 400 °C–425 °C and a higher temperature. The surface of the catalyst and its adsorbates were well characterized with ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and in situ infrared spectroscopy (IR). In situ studies of the surface of NiFe2O4 using AP-XPS suggest the formation of methoxy-like and formate-like intermediates at a temperature lower than 200 °C, supported by the observed vibrational signatures in in situ IR studies. Evolutions of C1s photoemission features and the nominal atomic ratios of C/(Ni + Fe) of the catalyst surface suggest that the formate-like intermediate is transformed to product molecules CO2 and H2O in the temperature range of 250–300 °C. In situ studies suggest the formation of a spectator, – Olattice – CH2 – Olattice –. It strongly bonds to surface through C–O bonds and cannot be activated even at 400 °C.

  4. Magnetic core-shell nano-TiO2/Al2O3/NiFe2O4 microparticles with enhanced photocatalytic activity.

    PubMed

    Jing, Mao-Xiang; Han, Chong; Wang, Zhou; Shen, Xiang-Qian

    2013-07-01

    The core-shell nano-TiO2/Al2O3/NiFe2O4 microparticles of 5-8 microm were prepared by the heterogeneous precipitation followed by calcination treatment. The morphologies, structure, crystalline phase, and magnetic property were characterized by optical biomicroscopy (OBM), scanning electron microscopy (SEM), X-ray diffractometry (XRD) and vibrating sample magnetometer (VSM) respectively. The photocatalytic activity was evaluated by degrading methyl orange solution either under UV light and sunlight. The results indicate that the nano-TiO2 layer consists of needle-like nanoparticles and the intermediate layer of Al2O3 avoids the nano-TiO2 agglomeration, shedding and uneven loading. The nano-TiO2/Al2O3/NiFe2O4 composite particles show high magnetization of 31.5 emu/g and enhanced photocatalytic activity to completely degrade 50 mg/L methyl orange solution either under UV light and sun light. The enhanced activity of the composite is attributed to the unique structure, insulation effect of Al2O3 intermediate layer and the hybrid effect of anatase TiO2 and NiFe2O4. The obtained catalyst may be magnetically separable and useful for many practical applications due to the improved photocatalytic properties under sunlight. PMID:23901515

  5. Impact of interface manipulation of oxide on electrical transport properties and low-frequency noise in MgO/NiFe/MgO heterojunctions

    SciTech Connect

    Li, Jian-wei; Zhao, Chong-jun; Feng, Chun; Yu, Guang-hua; Zhou, Zhongfu

    2015-08-15

    Low-frequency noise and magnetoresistance in sputtered-deposited Ta(5 nm)/MgO (3 nm)/NiFe(10 nm)/MgO(3 nm)/Ta(3 nm) films have been measured as a function of different annealing times at 400°C. These measurements did not change synchronously with annealing time. A significant increase in magnetoresistance is observed for short annealing times (of the order of minutes) and is correlated with a relatively small reduction in 1/f noise. In contrast, a significant reduction in 1/f noise is observed for long annealing times (of the order of hours) accompanied by a small change in magnetoresistance. After annealing for 2 hours, the 1/f noise decreases by three orders of magnitude. Transmission electron microscopy and slow positron annihilation results implicate the cause being micro-structural changes in the MgO layers and interfaces following different annealing times. The internal vacancies in the MgO layers gather into vacancy clusters to reduce the defect density after short annealing times, whereas the MgO/NiFe and the NiFe/MgO interfaces improve significantly after long annealing times with the amorphous MgO layers gradually crystallizing following the release of interfacial stress.

  6. Elastic and hierarchical porous carbon nanofibrous membranes incorporated with NiFe2O4 nanocrystals for highly efficient capacitive energy storage.

    PubMed

    Ge, Jianlong; Fan, Gang; Si, Yang; He, Jianxin; Kim, Hak-Yong; Ding, Bin; Al-Deyab, Salem S; El-Newehy, Mohamed; Yu, Jianyong

    2016-01-28

    Flexible membranes created from porous carbon nanofibers (CNFs) hold great promise in the next generation wearable energy storage devices, but challenges still remain due to the poor mechanical properties of porous carbon nanofibers. Here, we report a facile strategy to fabricate elastic and hierarchical porous CNF membranes with NiFe2O4 nanocrystals embedded via multicomponent electrospinning and nano-doping methods. Benefiting from the scattering effect of NiFe2O4 nanocrystals and graphitized carbon layers for the condensed stress, the resultant CNF membranes exhibit an enhanced elasticity with a bending radius <12 μm, rapid recovery from the deformations, and a superior softness. Quantitative pore size distribution and fractal analysis reveal that the CNFs possessed tunable porous structures with a high surface area of 493 m(2) g(-1) and a pore volume of 0.31 cm(3) g(-1). Benefiting from the robust mechanical stability, hierarchical porous structures and good electrochemical properties, the NiFe2O4 doped CNF membranes demonstrate a high electrical capacitance of 343 F g(-1), and good reversibility with a cycling efficiency of 97.4% even after 10,000 cycles. The successful synthesis of elastic porous CNF membranes also provided a versatile platform for the design and development of functional CNF based materials for various applications. PMID:26731700

  7. Characterization of carbon nanotubes decorated with NiFe2O4 magnetic nanoparticles as a novel electrochemical sensor: application for highly selective determination of sotalol using voltammetry.

    PubMed

    Ensafi, Ali A; Allafchian, Ali R; Rezaei, B; Mohammadzadeh, R

    2013-01-01

    A magnetic nano-composite of multiwall carbon nanotube, decorated with NiFe2O4 nanoparticles, was synthesized with citrate sol-gel method. The multiwall carbon nanotubes decorated with NiFe2O4 nanoparticles (NiFe2O4-MWCNTs) were characterized with different methods such as Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), atomic force microscopy (AFM), vibrating sample magnetometer (VSM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The new nano-composite acts as a suitable electrocatalyst for the oxidation of sotalol at a potential of 500 mV at the surface of the modified electrode. Linear sweep voltammetry exhibited two wide linear dynamic ranges of 0.5-1000 μmol L(-1) sotalol with a detection limit of 0.09 μmol L(-1). The modified electrode was used as a novel electrochemical sensor for the determination of sotalol in real samples such as pharmaceutical, patient and safe human urine.

  8. Monodisperse core/shell Ni/FePt nanoparticles and their con-version to Ni/Pt to catalyze oxygen reduction

    DOE PAGESBeta

    Zhang, Sen; Hao, Yizhou; Su, Dong; Doan-Nguyen, Vicky V. T.; Wu, Yaoting; Li, Jing; Sun, Shouheng; Murray, Christopher B.

    2014-10-28

    We report a size-controllable synthesis of monodisperse core/shell Ni/FePt nanoparticles (NPs) via a seed-mediated growth and their subsequent conversion to Ni/Pt NPs. Preventing surface oxidation of the Ni seeds is essential for the growth of uniform FePt shells. These Ni/FePt NPs have a thin (≈ 1 nm) FePt shell, and can be converted to Ni/Pt by acetic acid wash to yield active catalysts for oxygen reduction reaction (ORR). Tuning the core size allow for optimization of their electrocatalytic activity. The specific activity and mass activity of 4.2 nm/0.8 nm core/shell Ni/FePt reach 1.95 mA/cm² and 490 mA/mgPt at 0.9 Vmore » (vs. reversible hydrogen electrode, RHE), which are much higher than those of benchmark commercial Pt catalyst (0.34 mA/cm² and 92 mA/mgPt at 0.9 V). Our studies provide a robust approach to monodisperse core/shell NPs with non-precious metal core, making it possible to develop advanced NP catalysts with ultralow Pt content for ORR and many other heterogeneous reactions.« less

  9. Monodisperse core/shell Ni/FePt nanoparticles and their con-version to Ni/Pt to catalyze oxygen reduction

    SciTech Connect

    Zhang, Sen; Hao, Yizhou; Su, Dong; Doan-Nguyen, Vicky V. T.; Wu, Yaoting; Li, Jing; Sun, Shouheng; Murray, Christopher B.

    2014-10-28

    We report a size-controllable synthesis of monodisperse core/shell Ni/FePt nanoparticles (NPs) via a seed-mediated growth and their subsequent conversion to Ni/Pt NPs. Preventing surface oxidation of the Ni seeds is essential for the growth of uniform FePt shells. These Ni/FePt NPs have a thin (≈ 1 nm) FePt shell, and can be converted to Ni/Pt by acetic acid wash to yield active catalysts for oxygen reduction reaction (ORR). Tuning the core size allow for optimization of their electrocatalytic activity. The specific activity and mass activity of 4.2 nm/0.8 nm core/shell Ni/FePt reach 1.95 mA/cm² and 490 mA/mgPt at 0.9 V (vs. reversible hydrogen electrode, RHE), which are much higher than those of benchmark commercial Pt catalyst (0.34 mA/cm² and 92 mA/mgPt at 0.9 V). Our studies provide a robust approach to monodisperse core/shell NPs with non-precious metal core, making it possible to develop advanced NP catalysts with ultralow Pt content for ORR and many other heterogeneous reactions.

  10. Engineering of high performance supercapacitor electrode based on Fe-Ni/Fe2O3-NiO core/shell hybrid nanostructures

    NASA Astrophysics Data System (ADS)

    Singh, Ashutosh K.; Mandal, Kalyan

    2015-03-01

    The present work reports on fabrication and supercapacitor applications of a core/shell Fe-Ni/Fe2O3-NiO hybrid nanostructures (HNs) electrode. The core/shell Fe-Ni/Fe2O3-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 Fe2O3) 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, which helps in the superior electrochemical performance. The core/shell Fe-Ni/Fe2O3-NiO hybrid nanostructures electrode based supercapacitor shows very good electrochemical performances in terms of high specific capacitance nearly 1415 F g-1 at a current density of 2.5 A g-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.

  11. Tunable magnetocaloric effect in transition metal alloys

    PubMed Central

    Belyea, Dustin D.; Lucas, M. S.; Michel, E.; Horwath, J.; Miller, Casey W.

    2015-01-01

    The unpredictability of geopolitical tensions and resulting supply chain and pricing instabilities make it imperative to explore rare earth free magnetic materials. As such, we have investigated fully transition metal based “high entropy alloys” in the context of the magnetocaloric effect. We find the NiFeCoCrPdx family exhibits a second order magnetic phase transition whose critical temperature is tunable from 100 K to well above room temperature. The system notably displays changes in the functionality of the magnetic entropy change depending on x, which leads to nearly 40% enhancement of the refrigerant capacity. A detailed statistical analysis of the universal scaling behavior provides direct evidence that heat treatment and Pd additions reduce the distribution of exchange energies in the system, leading to a more magnetically homogeneous alloy. The general implications of this work are that the parent NiFeCoCr compound can be tuned dramatically with FCC metal additives. Together with their relatively lower cost, their superior mechanical properties that aid manufacturability and their relative chemical inertness that aids product longevity, NiFeCoCr-based materials could ultimately lead to commercially viable magnetic refrigerants. PMID:26507636

  12. Tunable magnetocaloric effect in transition metal alloys

    NASA Astrophysics Data System (ADS)

    Belyea, Dustin D.; Lucas, M. S.; Michel, E.; Horwath, J.; Miller, Casey W.

    2015-10-01

    The unpredictability of geopolitical tensions and resulting supply chain and pricing instabilities make it imperative to explore rare earth free magnetic materials. As such, we have investigated fully transition metal based “high entropy alloys” in the context of the magnetocaloric effect. We find the NiFeCoCrPdx family exhibits a second order magnetic phase transition whose critical temperature is tunable from 100 K to well above room temperature. The system notably displays changes in the functionality of the magnetic entropy change depending on x, which leads to nearly 40% enhancement of the refrigerant capacity. A detailed statistical analysis of the universal scaling behavior provides direct evidence that heat treatment and Pd additions reduce the distribution of exchange energies in the system, leading to a more magnetically homogeneous alloy. The general implications of this work are that the parent NiFeCoCr compound can be tuned dramatically with FCC metal additives. Together with their relatively lower cost, their superior mechanical properties that aid manufacturability and their relative chemical inertness that aids product longevity, NiFeCoCr-based materials could ultimately lead to commercially viable magnetic refrigerants.

  13. The oxidation performance of modern high-temperature alloys

    NASA Astrophysics Data System (ADS)

    Deodeshmukh, V. P.; Srivastava, S. K.

    2009-07-01

    The high-temperature oxidation resistance of an alloy is a key design criterion for components in a variety of industrial applications, such as advanced gas turbines, industrial heating, automotive, waste incineration, power generation and energy conversion, chemical and petrochemical processing, and metals and minerals processing. The importance of correctly assessing the long-term oxidation behavior of high-temperature alloys is illustrated. As applications move to higher temperatures, new alloys are needed. In this paper, the oxidation performance of three newly developed alloys, an alumina-forming Ni-Fe-Cr-Al alloy, a γ'-strengthened Ni-Cr-Co-Mo-(Al+Ti) alloy, and a nitride-strengthened Co-Cr-Fe-Ni-(Ti+Nb) alloy is presented.

  14. Synthesis of Nano-Crystalline Gamma-TiAl Materials

    NASA Technical Reports Server (NTRS)

    Hales, Stephen J.; Vasquez, Peter

    2003-01-01

    One of the principal problems with nano-crystalline materials is producing them in quantities and sizes large enough for valid mechanical property evaluation. The purpose of this study was to explore an innovative method for producing nano-crystalline gamma-TiAl bulk materials using high energy ball milling and brief secondary processes. Nano-crystalline powder feedstock was produced using a Fritsch P4(TM) vario-planetary ball mill recently installed at NASA-LaRC. The high energy ball milling process employed tungsten carbide tooling (vials and balls) and no process control agents to minimize contamination. In a collaborative effort, two approaches were investigated, namely mechanical alloying of elemental powders and attrition milling of pre-alloyed powders. The objective was to subsequently use RF plasma spray deposition and short cycle vacuum hot pressing in order to effect consolidation while retaining nano-crystalline structure in bulk material. Results and discussion of the work performed to date are presented.

  15. Ordered mesoporous MFe(2)O(4) (M = Co, Cu, Mg, Ni, Zn) thin films with nanocrystalline walls, uniform 16 nm diameter pores and high thermal stability: template-directed synthesis and characterization of redox active trevorite.

    PubMed

    Haetge, Jan; Suchomski, Christian; Brezesinski, Torsten

    2010-12-20

    In this paper, we report on ordered mesoporous NiFe(2)O(4) thin films synthesized via co-assembly of hydrated ferric nitrate and nickel chloride with an amphiphilic diblock copolymer, referred to as KLE. We establish that the NiFe(2)O(4) samples are highly crystalline after calcination at 600 °C, and that the conversion of the amorphous inorganic framework comes at little cost to the ordering of the high quality cubic network of pores averaging 16 nm in diameter. We further show that the synthesis method employed in this work can be readily extended to other ferrites, such as CoFe(2)O(4), CuFe(2)O(4), MgFe(2)O(4), and ZnFe(2)O(4), which could pave the way for innovative device design. While this article focuses on the self-assembly and characterization of these materials using various state-of-the-art techniques, including electron microscopy, grazing incidence small-angle X-ray scattering (GISAXS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), X-ray photoelectron spectroscopy (XPS), as well as UV-vis and Raman spectroscopy, we also examine the electrochemical properties and show the benefits of combining a continuous mesoporosity with nanocrystalline films. KLE-templated NiFe(2)O(4) electrodes exhibit reasonable levels of lithium ion storage at short charging times which stem from facile pseudocapacitance.

  16. Overproduction of the membrane-bound [NiFe]-hydrogenase in Thermococcus kodakarensis and its effect on hydrogen production

    PubMed Central

    Kanai, Tamotsu; Simons, Jan-Robert; Tsukamoto, Ryohei; Nakajima, Akihito; Omori, Yoshiyuki; Matsuoka, Ryoji; Beppu, Haruki; Imanaka, Tadayuki; Atomi, Haruyuki

    2015-01-01

    The hyperthermophilic archaeon Thermococcus kodakarensis can utilize sugars or pyruvate for growth. In the absence of elemental sulfur, the electrons via oxidation of these substrates are accepted by protons, generating molecular hydrogen (H2). The hydrogenase responsible for this reaction is a membrane-bound [NiFe]-hydrogenase (Mbh). In this study, we have examined several possibilities to increase the protein levels of Mbh in T. kodakarensis by genetic engineering. Highest levels of intracellular Mbh levels were achieved when the promoter of the entire mbh operon (TK2080-TK2093) was exchanged to a strong constitutive promoter from the glutamate dehydrogenase gene (TK1431) (strain MHG1). When MHG1 was cultivated under continuous culture conditions using pyruvate-based medium, a nearly 25% higher specific hydrogen production rate (SHPR) of 35.3 mmol H2 g-dcw−1 h−1 was observed at a dilution rate of 0.31 h−1. We also combined mbh overexpression using an even stronger constitutive promoter from the cell surface glycoprotein gene (TK0895) with disruption of the genes encoding the cytosolic hydrogenase (Hyh) and an alanine aminotransferase (AlaAT), both of which are involved in hydrogen consumption (strain MAH1). At a dilution rate of 0.30 h−1, the SHPR was 36.2 mmol H2 g-dcw−1 h−1, corresponding to a 28% increase compared to that of the host T. kodakarensis strain. Increasing the dilution rate to 0.83 h−1 or 1.07 h−1 resulted in a SHPR of 120 mmol H2 g-dcw−1 h−1, which is one of the highest production rates observed in microbial fermentation. PMID:26379632

  17. Influence of particle size on H2 and H2S sensing characteristics of nanocrystalline nickel ferrite

    NASA Astrophysics Data System (ADS)

    Ghosh, P.; Mukherjee, A.; Fu, M.; Chattopadhyay, S.; Mitra, P.

    2015-11-01

    Nanocrystalline nickel ferrite (NiFe2O4) was synthesized by sol-gel self-combustion technique. Ball milling at room temperature was carried out to control the particle size. Characterization of synthesized powders was made using X-ray diffraction (XRD) and Transmission electron microscopy (TEM) analysis. Fine powder resulted from milling was used to prepare gas sensing elements in pellet form. The gas-sensing properties were studied in presence of hydrogen and hydrogen sulfide as test gases. The gas-response was found to be strongly influenced by the particle size. Significantly high sensitivity of ~75% was found for ~5.35 nm nickel ferrite in presence of 200 ppm H2 S at an operating temperature of 150 °C. Sensitivity was found to increase with temperature before being maximum at a particular operating temperature.

  18. Oxidation resistant nanocrystalline MCrAl(Y) coatings and methods of forming such coatings

    DOEpatents

    Cheruvu, Narayana S.; Wei, Ronghua

    2014-07-29

    The present disclosure relates to an oxidation resistant nanocrystalline coating and a method of forming an oxidation resistant nanocrystalline coating. An oxidation resistant coating comprising an MCrAl(Y) alloy may be deposited on a substrate, wherein M, includes iron, nickel, cobalt, or combinations thereof present greater than 50 wt % of the MCrAl(Y) alloy, chromium is present in the range of 15 wt % to 30 wt % of the MCrAl(Y) alloy, aluminum is present in the range of 6 wt % to 12 wt % of the MCrAl(Y) alloy and yttrium, is optionally present in the range of 0.1 wt % to 0.5 wt % of the MCrAl(Y) alloy. In addition, the coating may exhibit a grain size of 200 nm or less as deposited.

  19. Microstructure and Fracture Behavior of Tungsten Heavy Alloys

    SciTech Connect

    Sunwoo, A

    2003-06-01

    The 93% W-5.6% Ni-1.4% Fe and 93.1% W-4.7% Ni-2.2% Co alloys (WHA) provided by Army Research Laboratory (ARL), Aberdeen are characterized to determine the effects of matrix alloying and swaging on the microstructure and fracture behavior. The W particles are oblong with respect to the swaging direction. The microstructure of the W-Ni-Fe alloy reveals good cohesive bonding between W particles, but there is W-matrix interface separation and matrix alloy cracking. The microstructure of the W-Ni-Co alloy reveals regions of good cohesive bonding between W particles, but also regions where some wetting has not occurred by the liquid. No evidence was observed of matrix alloy cracking. The fracture characteristic of WHA is dominantly cleavage of W particles.

  20. Elastic and hierarchical porous carbon nanofibrous membranes incorporated with NiFe2O4 nanocrystals for highly efficient capacitive energy storage

    NASA Astrophysics Data System (ADS)

    Ge, Jianlong; Fan, Gang; Si, Yang; He, Jianxin; Kim, Hak-Yong; Ding, Bin; Al-Deyab, Salem S.; El-Newehy, Mohamed; Yu, Jianyong

    2016-01-01

    Flexible membranes created from porous carbon nanofibers (CNFs) hold great promise in the next generation wearable energy storage devices, but challenges still remain due to the poor mechanical properties of porous carbon nanofibers. Here, we report a facile strategy to fabricate elastic and hierarchical porous CNF membranes with NiFe2O4 nanocrystals embedded via multicomponent electrospinning and nano-doping methods. Benefiting from the scattering effect of NiFe2O4 nanocrystals and graphitized carbon layers for the condensed stress, the resultant CNF membranes exhibit an enhanced elasticity with a bending radius <12 μm, rapid recovery from the deformations, and a superior softness. Quantitative pore size distribution and fractal analysis reveal that the CNFs possessed tunable porous structures with a high surface area of 493 m2 g-1 and a pore volume of 0.31 cm3 g-1. Benefiting from the robust mechanical stability, hierarchical porous structures and good electrochemical properties, the NiFe2O4 doped CNF membranes demonstrate a high electrical capacitance of 343 F g-1, and good reversibility with a cycling efficiency of 97.4% even after 10 000 cycles. The successful synthesis of elastic porous CNF membranes also provided a versatile platform for the design and development of functional CNF based materials for various applications.Flexible membranes created from porous carbon nanofibers (CNFs) hold great promise in the next generation wearable energy storage devices, but challenges still remain due to the poor mechanical properties of porous carbon nanofibers. Here, we report a facile strategy to fabricate elastic and hierarchical porous CNF membranes with NiFe2O4 nanocrystals embedded via multicomponent electrospinning and nano-doping methods. Benefiting from the scattering effect of NiFe2O4 nanocrystals and graphitized carbon layers for the condensed stress, the resultant CNF membranes exhibit an enhanced elasticity with a bending radius <12 μm, rapid recovery

  1. Vapor phase oxidation of benzoic acid to phenol over a novel catalyst system consisting of NiO and NiFe{sub 2}O{sub 4}

    SciTech Connect

    Miki, Jun; Asanuma, Minoru; Tachibana, Yakudo

    1995-02-01

    NiO and Fe{sub 2}O{sub 3} were found to show the catalytic activities for the vapor phase oxidation of benzoic acid to form phenol. Furthermore, the enhancement of the activity and phenol selectivity were achieved by combined Ni and Fe components prepared by precipitation. The calcination temperature and the atomic ratio of Ni to Fe were found to be important for the enhancement of activity. The homogeneous distribution profile of NiO and NiFe{sub 2}O{sub 4} on the surface and in the bulk of the catalyst is essential for the optimization of phenol formation. 32 refs., 7 figs., 4 tabs.

  2. Mechanism of H2 Production by Models for the [NiFe]-Hydrogenases: Role of Reduced Hydrides.

    PubMed

    Ulloa, Olbelina A; Huynh, Mioy T; Richers, Casseday P; Bertke, Jeffery A; Nilges, Mark J; Hammes-Schiffer, Sharon; Rauchfuss, Thomas B

    2016-07-27

    The intermediacy of a reduced nickel-iron hydride in hydrogen evolution catalyzed by Ni-Fe complexes was verified experimentally and computationally. In addition to catalyzing hydrogen evolution, the highly basic and bulky (dppv)Ni(μ-pdt)Fe(CO)(dppv) ([1](0); dppv = cis-C2H2(PPh2)2) and its hydride derivatives have yielded to detailed characterization in terms of spectroscopy, bonding, and reactivity. The protonation of [1](0) initially produces unsym-[H1](+), which converts by a first-order pathway to sym-[H1](+). These species have C1 (unsym) and Cs (sym) symmetries, respectively, depending on the stereochemistry of the octahedral Fe site. Both experimental and computational studies show that [H1](+) protonates at sulfur. The S = 1/2 hydride [H1](0) was generated by reduction of [H1](+) with Cp*2Co. Density functional theory (DFT) calculations indicate that [H1](0) is best described as a Ni(I)-Fe(II) derivative with significant spin density on Ni and some delocalization on S and Fe. EPR spectroscopy reveals both kinetic and thermodynamic isomers of [H1](0). Whereas [H1](+) does not evolve H2 upon protonation, treatment of [H1](0) with acids gives H2. The redox state of the "remote" metal (Ni) modulates the hydridic character of the Fe(II)-H center. As supported by DFT calculations, H2 evolution proceeds either directly from [H1](0) and external acid or from protonation of the Fe-H bond in [H1](0) to give a labile dihydrogen complex. Stoichiometric tests indicate that protonation-induced hydrogen evolution from [H1](0) initially produces [1](+), which is reduced by [H1](0). Our results reconcile the required reductive activation of a metal hydride and the resistance of metal hydrides toward reduction. This dichotomy is resolved by reduction of the remote (non-hydride) metal of the bimetallic unit. PMID:27328053

  3. Role of nanocrystalline cerium oxide coatings on austenitic stainless steels

    NASA Astrophysics Data System (ADS)

    Zhang, Haiying

    Protective nanocrystalline cerium oxide coating has been applied to ASTM grade 304L and 304 austenitic stainless steels to improve its oxidation resistance at elevated temperatures. Experimentally, the selected alloy was exposed to 800°C/1000°C under dry air conditions. Weight changes (DeltaW/A) were monitored as a function of time and the results were compared with uncoated alloys tested under similar conditions. It was found that the oxidation resistances of 304L and 304 stainless steels were significantly improved. A comparison of the oxidation rates indicated that the nanocrystalline cerium oxide coating reduced the rate of oxidation by more than two orders of magnitude. Nevertheless, a comprehensive understanding of the mechanisms responsible for the reduction in the oxidation rate is not clear. Consequently, this work is aimed at investigating the mechanisms involved during scale growth in the presence or absence of nanocrystalline coatings. For this purpose, density functional theory was carried out in order to predict oxygen and iron diffusion microscopic activation energies and reveal the intrinsic characteristics of nanocrystalline coatings. A numerical simulation of corrosion process has also been conducted to predict the corrosion rates of alloys with and without coatings. Hence, the results from simulations are compared with the experimental outcome, and possible explanations are given to account for the reduction in the exhibited oxidation rates. The simulation results will provide a highly valuable tool for the realization of functional nanostructures and architectures "by design", particularly in the development of novel coatings, and a new approach of life assessment.

  4. Nanocrystalline nanowires: III. Electrons.

    PubMed

    Allen, Philip B

    2007-05-01

    Nanocrystalline nanowires (NCNW) are fragments of bulk crystals that are infinite in only one direction and typically have some rotational symmetry around this direction. Electron eigenstates belonging to the symmetry labels (k,m) (wavevector and rotational quantum number) are discussed. The rotational quantum number simplifies discussion of optical properties. For m not equal 0, the +/-m degeneracy allows orbital magnetism. The simplest sensible model which is more complex than a one-dimensional chain is solved. Methods are suggested for incorporating rotational symmetry into preexisting codes with three-dimensional translations.

  5. Nanocrystalline nanowires: 2. Phonons.

    PubMed

    Allen, Philip B

    2007-01-01

    Nanocrystalline nanowires (NCNW) are fragments of bulk crystals that are infinite in only one direction. A construction is given for calculating eigenstates belonging to the symmetry labels (k,m) (wavevector and rotational quantum number). Vibrational harmonic eigenstates are worked out explicitly for a simple model, illustrating the general results: the LA mode has m=0, while with sufficient rotational symmetry, the TA branch is doubly degenerate, has m=+/-1, and has quadratic dispersion with k for k less than the reciprocal diameter of the NCNW. The twiston branch (a fourth Goldstone boson) is an acoustic m=0 branch, additional to the LA and two TA branches.

  6. Magnetism in nanocrystalline gold.

    PubMed

    Tuboltsev, Vladimir; Savin, Alexander; Pirojenko, Alexandre; Räisänen, Jyrki

    2013-08-27

    While bulk gold is well known to be diamagnetic, there is a growing body of convincing experimental and theoretical work indicating that nanostructured gold can be imparted with unconventional magnetic properties. Bridging the current gap in experimental study of magnetism in bare gold nanomaterials, we report here on magnetism in gold nanocrystalline films produced by cluster deposition in the aggregate form that can be considered as a crossover state between a nanocluster and a continuous film. We demonstrate ferromagnetic-like hysteretic magnetization with temperature dependence indicative of spin-glass-like behavior and find this to be consistent with theoretical predictions, available in the literature, based on first-principles calculations.

  7. Linking stress-driven microstructural evolution in nanocrystalline aluminium with grain boundary doping of oxygen.

    PubMed

    He, Mo-Rigen; Samudrala, Saritha K; Kim, Gyuseok; Felfer, Peter J; Breen, Andrew J; Cairney, Julie M; Gianola, Daniel S

    2016-01-01

    The large fraction of material residing at grain boundaries in nanocrystalline metals and alloys is responsible for their ultrahigh strength, but also undesirable microstructural instability under thermal and mechanical loads. However, the underlying mechanism of stress-driven microstructural evolution is still poorly understood and precludes rational alloy design. Here we combine quantitative in situ electron microscopy with three-dimensional atom-probe tomography to directly link the mechanics and kinetics of grain boundary migration in nanocrystalline Al films with the excess of O atoms at the boundaries. Site-specific nanoindentation leads to grain growth that is retarded by impurities, and enables quantification of the critical stress for the onset of grain boundary migration. Our results show that a critical excess of impurities is required to stabilize interfaces in nanocrystalline materials against mechanical driving forces, providing new insights to guide control of deformation mechanisms and tailoring of mechanical properties apart from grain size alone. PMID:27071458

  8. Linking stress-driven microstructural evolution in nanocrystalline aluminium with grain boundary doping of oxygen

    NASA Astrophysics Data System (ADS)

    He, Mo-Rigen; Samudrala, Saritha K.; Kim, Gyuseok; Felfer, Peter J.; Breen, Andrew J.; Cairney, Julie M.; Gianola, Daniel S.

    2016-04-01

    The large fraction of material residing at grain boundaries in nanocrystalline metals and alloys is responsible for their ultrahigh strength, but also undesirable microstructural instability under thermal and mechanical loads. However, the underlying mechanism of stress-driven microstructural evolution is still poorly understood and precludes rational alloy design. Here we combine quantitative in situ electron microscopy with three-dimensional atom-probe tomography to directly link the mechanics and kinetics of grain boundary migration in nanocrystalline Al films with the excess of O atoms at the boundaries. Site-specific nanoindentation leads to grain growth that is retarded by impurities, and enables quantification of the critical stress for the onset of grain boundary migration. Our results show that a critical excess of impurities is required to stabilize interfaces in nanocrystalline materials against mechanical driving forces, providing new insights to guide control of deformation mechanisms and tailoring of mechanical properties apart from grain size alone.

  9. Linking stress-driven microstructural evolution in nanocrystalline aluminium with grain boundary doping of oxygen

    PubMed Central

    He, Mo-Rigen; Samudrala, Saritha K.; Kim, Gyuseok; Felfer, Peter J.; Breen, Andrew J.; Cairney, Julie M.; Gianola, Daniel S.

    2016-01-01

    The large fraction of material residing at grain boundaries in nanocrystalline metals and alloys is responsible for their ultrahigh strength, but also undesirable microstructural instability under thermal and mechanical loads. However, the underlying mechanism of stress-driven microstructural evolution is still poorly understood and precludes rational alloy design. Here we combine quantitative in situ electron microscopy with three-dimensional atom-probe tomography to directly link the mechanics and kinetics of grain boundary migration in nanocrystalline Al films with the excess of O atoms at the boundaries. Site-specific nanoindentation leads to grain growth that is retarded by impurities, and enables quantification of the critical stress for the onset of grain boundary migration. Our results show that a critical excess of impurities is required to stabilize interfaces in nanocrystalline materials against mechanical driving forces, providing new insights to guide control of deformation mechanisms and tailoring of mechanical properties apart from grain size alone. PMID:27071458

  10. Electric field tuning of non-volatile three-state magnetoelectric memory in FeCo-NiFe2O4/Pb(Mg1/3Nb2/3)0.7Ti0.3O3 heterostructures

    NASA Astrophysics Data System (ADS)

    Jiang, Changjun; Zhang, Chao; Dong, Chunhui; Guo, Dangwei; Xue, Desheng

    2015-03-01

    We demonstrate electric field impulse-induced reversible tristable magnetization switching in FeCo-NiFe2O4/Pb(Mg1/3Nb2/3)0.7Ti0.3O3 (PMN-PT) heterostructures at room temperature. The magnetic properties of the FeCo-NiFe2O4 film can be changed reversibly by the strain-mediated magnetoelectric coupling effect. Three piezostrain-mediated reversible and stable electric resistance states were obtained in the FeCo-NiFe2O4 film when different electric field impulses were applied, including large positive and negative fields and an impulse that was smaller than the electric coercive field. Consequently, reversible electric field impulse tuning of the tristable resistance state, which is related to the different magnetization switching properties of the materials, was realized. These results provide a promising approach for low loss multistate magnetoelectric memory devices for information storage applications.

  11. Effect of MgO spacer and annealing on interface and magnetic properties of ion beam sputtered NiFe/Mg/MgO/CoFe layer structures

    SciTech Connect

    Bhusan Singh, Braj; Chaudhary, Sujeet

    2012-09-15

    The effect of variation in the thickness of ion assisted ion beam sputtered MgO spacer layer deposited at oxygen ion assisted energy of 50 eV on the extent of magnetic coupling of NiFe and CoFe layers in Si/NiFe(10 nm)/Mg(1 nm)/MgO(2,4,6 nm)/CoFe(10 nm) sandwich structure is investigated. At MgO spacer layer thickness of 4 nm, the separate reversal of magnetizations of the two ferromagnetic layers is observed in the hystresis loop recorded along easy direction. This results in a 3.5 Oe wide plateau like region during magnetization reversal, which became 4.5 Oe at 6 nm thin MgO. At 2 nm thin MgO, the absence of plateau during magnetization reversal region revealed ferromagnetic coupling between the two ferromagnetic layers, which is understood to arise due to the growth of very thin and low density (1.22 gm/cc) MgO spacer layer, indicating the presence of pinholes as revealed by x-ray reflectometry. After vaccum annealing (200 Degree-Sign C/1 h), the plateau region for 4 and 6 nm thin MgO case decreased to 1.5 Oe and 2.0 Oe, respectively, due to enhanced interface roughness/mixing. In addition, an enhancement of the in-plane magnetic anisotropy is also observed.

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

    SciTech Connect

    Chen, Xi; Wang, Shouguo Han, Gang; Jiang, Shaolong; Yang, Kang; Liu, Qianqian; Yu, Guanghua; Liu, Jialong; Wang, Rongming

    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 acting 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.

  13. Microstructural changes in NiFe2O4 ceramics prepared with powders derived from different fuels in sol-gel auto-combustion technique

    NASA Astrophysics Data System (ADS)

    Chauhan, Lalita; Bokolia, Renuka; Sreenivas, K.

    2016-05-01

    Structural properties of Nickel ferrite (NiFe2O4) ceramics prepared from powders derived from sol gel auto-combustion method using different fuels (citric acid, glycine and Dl-alanine) are compared. Changes in the structural properties at different sintering temperatures are investigated. X-ray diffraction (XRD) confirms the formation of single phase material with cubic structure. Ceramics prepared using the different powders obtained from different fuels show that that there are no significant changes in lattice parameters. However increasing sintering temperatures show significant improvement in density and grain size. The DL-alanine fuel is found to be the most effective fuel for producing NIFe2O4 powders by the sol-gel auto combustion method and yields highly crystalline powders in the as-burnt stage itself at a low temperature (80 °C). Subsequent use of the powders in ceramic manufacturing produces dense NiFe2O4 ceramics with a uniform microstructure and a large grain size.

  14. De novo modeling of the F420-reducing [NiFe]-hydrogenase from a methanogenic archaeon by cryo-electron microscopy

    PubMed Central

    Mills, Deryck J; Vitt, Stella; Strauss, Mike; Shima, Seigo; Vonck, Janet

    2013-01-01

    Methanogenic archaea use a [NiFe]-hydrogenase, Frh, for oxidation/reduction of F420, an important hydride carrier in the methanogenesis pathway from H2 and CO2. Frh accounts for about 1% of the cytoplasmic protein and forms a huge complex consisting of FrhABG heterotrimers with each a [NiFe] center, four Fe-S clusters and an FAD. Here, we report the structure determined by near-atomic resolution cryo-EM of Frh with and without bound substrate F420. The polypeptide chains of FrhB, for which there was no homolog, was traced de novo from the EM map. The 1.2-MDa complex contains 12 copies of the heterotrimer, which unexpectedly form a spherical protein shell with a hollow core. The cryo-EM map reveals strong electron density of the chains of metal clusters running parallel to the protein shell, and the F420-binding site is located at the end of the chain near the outside of the spherical structure. DOI: http://dx.doi.org/10.7554/eLife.00218.001 PMID:23483797

  15. Electrochemical and Infrared Spectroscopic Studies Provide Insight into Reactions of the NiFe Regulatory Hydrogenase from Ralstonia eutropha with O2 and CO.

    PubMed

    Ash, Philip A; Liu, Juan; Coutard, Nathan; Heidary, Nina; Horch, Marius; Gudim, Ingvild; Simler, Thomas; Zebger, Ingo; Lenz, Oliver; Vincent, Kylie A

    2015-10-29

    The regulatory hydrogenase (RH) from Ralstonia eutropha acts as the H2-sensing unit of a two-component system that regulates biosynthesis of the energy conserving hydrogenases of the organism according to the availability of H2. The H2 oxidation activity, which was so far determined in vitro with artificial electron acceptors, has been considered to be insensitive to O2 and CO. It is assumed that bulky isoleucine and phenylalanine amino acid residues close to the NiFe active site "gate" gas access, preventing molecules larger than H2 interacting with the active site. We have carried out sensitive electrochemical measurements to demonstrate that O2 is in fact an inhibitor of H2 oxidation by the RH, and that both H(+) reduction and H2 oxidation are inhibited by CO. Furthermore, we have demonstrated that the inhibitory effect of O2 arises due to interaction of O2 with the active site. Using protein film infrared electrochemistry (PFIRE) under H2 oxidation conditions, in conjunction with solution infrared measurements, we have identified previously unreported oxidized inactive and catalytically active reduced states of the RH active site. These findings suggest that the RH has a rich active site chemistry similar to that of other NiFe hydrogenases. PMID:26115011

  16. Synthesis and characterization of the NiFe2O4@TEOS-TPS@Ag nanocomposite and investigation of its antibacterial activity

    NASA Astrophysics Data System (ADS)

    Allafchian, Ali R.; Jalali, S. A. H.; Amiri, R.; Shahabadi, Sh.

    2016-11-01

    In this study, the NiFe2O4 was embedded in (3-mercaptopropyl) trimethoxysilane (TPS) and tetraethyl orthosilicate (TEOS) using the sol-gel method. These compounds were used as the support of Ag nanoparticles (Ag NPs). The NiFe2O4@TEOS-TPS@Ag nanocomposites were obtained with the development of bonding between the silver atoms of Ag NPs and the sulfur atoms of TPS molecule. Field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) were used for the characterization of the Ag nanocomposites. Also, the magnetic properties of these nanocomposites were studied by using a vibrating sample magnetometer (VSM) technique. The disk diffusion, minimum inhibition concentration (MIC) and minimum bactericidal concentrations (MBC) tests were used for the investigation of the antibacterial effect of this nanocomposite against bacterial strains. The synthesized nanocomposite presented high reusability and good antibacterial activity against gram-positive and gram-negative bacteria. Remarkably, this nanocomposite could be easily removed from the disinfected media by magnetic decantation.

  17. Crystallization and preliminary X-ray crystallographic studies of the [NiFe] hydrogenase maturation proteins HypC and HypD

    SciTech Connect

    Watanabe, Satoshi; Matsumi, Rie; Atomi, Haruyuki; Imanaka, Tadayuki; Miki, Kunio

    2007-06-01

    The [NiFe] hydrogenase maturation proteins HypC and HypD were purified and crystallized. Crystals of HypC and HypD suitable for data collection diffracted to 1.80 and 2.07 Å resolution, respectively. HypC and HypD proteins are required for the insertion of the Fe atom with diatomic ligands into the large subunit of [NiFe] hydrogenases, an important step in the maturation process of this type of hydrogenase. The crystallization and preliminary crystallographic analysis of HypC and HypD from Thermococcus kodakaraensis KOD1 are reported. Crystals of HypC grew in two different forms. Monoclinic crystals of HypC in space group C2 with unit-cell parameters a = 78.2, b = 59.1, c = 54.0 Å, β = 109.0° were obtained using PEG 4000 and ammonium sulfate or sodium bromide as precipitants. They diffracted X-rays to 1.8 Å resolution and were suitable for structure determination. Crystals of HypD were also obtained in two different forms. The monoclinic crystals obtained using PEG 4000 and magnesium chloride diffracted X-rays to beyond 2.1 Å resolution, despite growing as clusters. They belong to space group P2{sub 1}, with unit-cell parameters a = 42.3, b = 118.4, c = 81.2 Å, β = 100.9°, and are suitable for data collection.

  18. Crystallization and preliminary X-ray crystallographic study of [NiFe]-hydrogenase maturation factor HypE from Thermococcus kodakaraensis KOD1

    SciTech Connect

    Arai, Takayuki; Watanabe, Satoshi; Matsumi, Rie; Atomi, Haruyuki; Imanaka, Tadayuki; Miki, Kunio

    2007-09-01

    The [NiFe]-hydrogenase maturation protein HypE was purified and crystallized. Crystals of HypE suitable for data collection diffracted to 1.55 Å resolution. The hydrogenase maturation protein HypE is involved in the biosynthesis of the CN ligands of the active-site iron of [NiFe] hydrogenases using carbamoylphosphate as a substrate. Here, the crystallization and preliminary crystallographic analysis of HypE from Thermococcus kodakaraensis KOD1 are reported. Crystals of HypE (338 amino acids, 35.9 kDa) have been obtained by the sitting-drop vapour-diffusion method using 2-methyl-2,4-pentanediol (MPD) as a precipitant. The crystals belong to space group P2{sub 1}2{sub 1}2, with unit-cell parameters a = 88.3, b = 45.8, c = 75.1 Å. There is one HypE molecule in the asymmetric unit. A complete native X-ray diffraction data set was collected to a maximum resolution of 1.55 Å at 100 K.

  19. Influence of carboxylic acid type on microstructure and magnetic properties of polymeric complex sol-gel driven NiFe2O4

    NASA Astrophysics Data System (ADS)

    Hessien, M. M.; Mostafa, Nasser Y.; Abd-Elkader, Omar H.

    2016-01-01

    Citric, oxalic and tartaric acids were used for synthesis of NiFe2O4 using polymeric complex precursor route. The dry precursor gels were calcined at various temperatures (400-1100 °C) for 2 h. All carboxylic acids produce iron-deficient NiFe2O4 with considerable amount of α-Fe2O3 at 400 °C. Increase in the annealing temperature caused reaction of α-Fe2O3 with iron-deficient ferrite phase. The amount of initially formed α-Fe2O3 is directly correlated with stability constant and inversely correlated with the decomposition temperature of Fe(III) carboxylate precursors. In case of tartaric acid precursor, single phase of the ferrite was obtained at 450 °C. However, in case of oxalic acid and citric acid precursors, single phase ferrite was obtained at 550 °C and 700 °C, respectively. The lattice parameters were increased with increasing annealing temperature and with decreasing the amount of α-Fe2O3. Maximum saturation magnetization (55 emu/g) was achieved using tartaric acid precursor annealed at 1100 °C.

  20. Magnetic, local ferroelectricity and magnetodielectric properties of NiFe2O4-poly (vinylidene-fluoride)-BaTiO3 composite film

    NASA Astrophysics Data System (ADS)

    Kumar, Amit; Yadav, K. L.

    2016-04-01

    We report the magnetic, dielectric, and magnetoelctric properties of NiFe2O4-poly (vinylidene-fluoride)-BaTiO3 composite film. The coercive field (±2H c ∼ 344 Oe) and remnant magnetization (M r ∼ 6.1 emu g‑1) were observed at room temperature. The dielectric permittivity at room temperature (ε‧RT ∼ 281) was found to decrease with increase in frequency. The magnetocapacitance was found to be ∼5.9% at an applied dc magnetic field of 8 kOe (frequency = 1 kHz). Magnetoelectric coupling coefficient (α E ∼ 4.1 mV cm‑1 Oe‑1) measured by dynamic method (at ac magnetic field = 30 Oe) is observed higher (two times) than those reported for some materials. In addition, we have observed the image of ferroelectric domain using piezoelectric force microscopy at room temperature. Large magnetodielectric/magnetoelectric response in this composite is possibly a result of the effective mechanical interaction between NiFe2O4 and BaTiO3 through the polymer matrix.

  1. Specific features of defect and mass transport in concentrated fcc alloys

    DOE PAGESBeta

    Osetsky, Yuri N.; Béland, Laurent K.; Stoller, Roger E.

    2016-06-15

    We report that diffusion and mass transport are basic properties that control materials performance, such as phase stability, solute decomposition and radiation tolerance. While understanding diffusion in dilute alloys is a mature field, concentrated alloys are much less studied. Here, atomic-scale diffusion and mass transport via vacancies and interstitial atoms are compared in fcc Ni, Fe and equiatomic Ni-Fe alloy. High temperature properties were determined using conventional molecular dynamics on the microsecond timescale, whereas the kinetic activation-relaxation (k-ART) approach was applied at low temperatures. The k-ART was also used to calculate transition states in the alloy and defect transport coefficients.more » The calculations reveal several specific features. For example, vacancy and interstitial defects migrate via different alloy components, diffusion is more sluggish in the alloy and, notably, mass transport in the concentrated alloy cannot be predicted on the basis of diffusion in its pure metal counterparts. Lastly, the percolation threshold for the defect diffusion in the alloy is discussed and it is suggested that this phenomenon depends on the properties and diffusion mechanisms of specific defects.« less

  2. Connecting [NiFe]- and [FeFe]-hydrogenases: mixed-valence nickel-iron dithiolates with rotated structures.

    PubMed

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

    2012-08-20

    New mixed-valence iron-nickel dithiolates are described that exhibit structures similar to those of mixed-valence diiron dithiolates. The interaction of tricarbonyl salt [(dppe)Ni(pdt)Fe(CO)(3)]BF(4) ([1]BF(4), where dppe = Ph(2)PCH(2)CH(2)PPh(2) and pdt(2-) = -SCH(2)CH(2)CH(2)S-) with P-donor ligands (L) afforded the substituted derivatives [(dppe)Ni(pdt)Fe(CO)(2)L]BF(4) incorporating L = PHCy(2) ([1a]BF(4)), PPh(NEt(2))(2) ([1b]BF(4)), P(NMe(2))(3) ([1c]BF(4)), P(i-Pr)(3) ([1d]BF(4)), and PCy(3) ([1e]BF(4)). The related precursor [(dcpe)Ni(pdt)Fe(CO)(3)]BF(4) ([2]BF(4), where dcpe = Cy(2)PCH(2)CH(2)PCy(2)) gave the more electron-rich family of compounds [(dcpe)Ni(pdt)Fe(CO)(2)L]BF(4) for L = PPh(2)(2-pyridyl) ([2a]BF(4)), PPh(3) ([2b]BF(4)), and PCy(3) ([2c]BF(4)). For bulky and strongly basic monophosphorus ligands, the salts feature distorted coordination geometries at iron: crystallographic analyses of [1e]BF(4) and [2c]BF(4) showed that they adopt "rotated" Fe(I) centers, in which PCy(3) occupies a basal site and one CO ligand partially bridges the Ni and Fe centers. Like the undistorted mixed-valence derivatives, members of the new class of complexes are described as Ni(II)Fe(I) (S = ½) systems according to electron paramagnetic resonance spectroscopy, although with attenuated (31)P hyperfine interactions. Density functional theory calculations using the BP86, B3LYP, and PBE0 exchange-correlation functionals agree with the structural and spectroscopic data, suggesting that the spin for [1e](+) is mostly localized in a Fe(I)-centered d(z(2)) orbital, orthogonal to the Fe-P bond. The PCy(3) complexes, rare examples of species featuring "rotated" Fe centers, both structurally and spectroscopically incorporate features from homobimetallic mixed-valence diiron dithiolates. Also, when the NiS(2)Fe core of the [NiFe]-hydrogenase active site is reproduced, the "hybrid models" incorporate key features of the two major classes of hydrogenase. Furthermore, cyclic

  3. Connecting [NiFe]- and [FeFe]-hydrogenases: mixed-valence nickel-iron dithiolates with rotated structures.

    PubMed

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

    2012-08-20

    New mixed-valence iron-nickel dithiolates are described that exhibit structures similar to those of mixed-valence diiron dithiolates. The interaction of tricarbonyl salt [(dppe)Ni(pdt)Fe(CO)(3)]BF(4) ([1]BF(4), where dppe = Ph(2)PCH(2)CH(2)PPh(2) and pdt(2-) = -SCH(2)CH(2)CH(2)S-) with P-donor ligands (L) afforded the substituted derivatives [(dppe)Ni(pdt)Fe(CO)(2)L]BF(4) incorporating L = PHCy(2) ([1a]BF(4)), PPh(NEt(2))(2) ([1b]BF(4)), P(NMe(2))(3) ([1c]BF(4)), P(i-Pr)(3) ([1d]BF(4)), and PCy(3) ([1e]BF(4)). The related precursor [(dcpe)Ni(pdt)Fe(CO)(3)]BF(4) ([2]BF(4), where dcpe = Cy(2)PCH(2)CH(2)PCy(2)) gave the more electron-rich family of compounds [(dcpe)Ni(pdt)Fe(CO)(2)L]BF(4) for L = PPh(2)(2-pyridyl) ([2a]BF(4)), PPh(3) ([2b]BF(4)), and PCy(3) ([2c]BF(4)). For bulky and strongly basic monophosphorus ligands, the salts feature distorted coordination geometries at iron: crystallographic analyses of [1e]BF(4) and [2c]BF(4) showed that they adopt "rotated" Fe(I) centers, in which PCy(3) occupies a basal site and one CO ligand partially bridges the Ni and Fe centers. Like the undistorted mixed-valence derivatives, members of the new class of complexes are described as Ni(II)Fe(I) (S = ½) systems according to electron paramagnetic resonance spectroscopy, although with attenuated (31)P hyperfine interactions. Density functional theory calculations using the BP86, B3LYP, and PBE0 exchange-correlation functionals agree with the structural and spectroscopic data, suggesting that the spin for [1e](+) is mostly localized in a Fe(I)-centered d(z(2)) orbital, orthogonal to the Fe-P bond. The PCy(3) complexes, rare examples of species featuring "rotated" Fe centers, both structurally and spectroscopically incorporate features from homobimetallic mixed-valence diiron dithiolates. Also, when the NiS(2)Fe core of the [NiFe]-hydrogenase active site is reproduced, the "hybrid models" incorporate key features of the two major classes of hydrogenase. Furthermore, cyclic

  4. Effect of aluminide particle distribution on the high temperature crack growth characteristics of a Co-Ni-Fe superalloy

    SciTech Connect

    Lyons, J.S.; Reynolds, A.P.; Clawson, J.D.

    1997-10-01

    Inconel 783{reg_sign} is an oxidant-resistant, controlled coefficient of thermal expansion, cobalt-nickel-iron-based superalloy. The matrix ({gamma}) is FCC and can be strengthened by coherent strengthening precipitates ({gamma}{prime}). It has been shown that an aluminum content greater than 5 wt% leads to the formation of body-centered aluminide ({beta}) particles and improved resistance to stress accelerated grain boundary oxygen (SAGBO) embrittlement relative to other low-expansion superalloys. The study described below was undertaken to determine the role of the {beta} phase during creep crack growth, and how its distribution affects the alloy`s SAGBO resistance. Aging of alloy 783 to produce a continuous grain boundary film of {beta} phase results in reduced creep crack growth rates at 538 C compared to heat treatments which do not result in a continuous film. Oxidation studies indicate that the {beta} phase is oxidation resistant and hence may cause increased resistance to SAGBO.

  5. Grain growth and structural relaxation of nanocrystalline Bi₂Te₃

    SciTech Connect

    Humphry-Baker, Samuel A.; Schuh, Christopher A.

    2014-10-21

    Recovery and grain growth behavior is investigated systematically for the nanocrystalline thermoelectric compound bismuth telluride, synthesized by mechanical alloying. During annealing treatments at elevated temperatures, structural evolution is tracked using x-ray diffraction, electron microscopy and calorimetry. Below a homologous temperature of about 0.6T{sub m}, grain growth occurs slowly with an activation energy of 89 kJ/mol. However above this temperature grain growth becomes more rampant with an activation energy of 242 kJ/mol. The transition is attributed to a shift from a relaxation or recovery process that includes some reordering of the grain boundary structure, to a more conventional diffusionally-limited grain growth process. By extrapolating the measured grain growth and microstrain evolution kinetics, a thermal budget map is constructed, permitting recommendations for improving the thermoelectric properties of nanocrystalline materials processed via a powder route.

  6. Nanocrystalline spinel ferrite (MFe{sub 2}O{sub 4}, M = Ni, Co, Mn, Mg, Zn) powders prepared by a simple aloe vera plant-extracted solution hydrothermal route

    SciTech Connect

    Phumying, Santi; Labuayai, Sarawuth; Swatsitang, Ekaphan; Amornkitbamrung, Vittaya; Maensiri, Santi

    2013-06-01

    Graphical abstract: This figure shows the specific magnetization curves of the as-prepared MFe{sub 2}O{sub 4} (M = Ni, Co, Mn, Mg, Zn) powders obtained from room temperature VSM measurement. These curves are typical for a soft magnetic material and indicate hysteresis ferromagnetism in the field ranges of ±500 Oe, ±1000 Oe, and ±2000 Oe for the CoFe{sub 2}O{sub 4}, MgFe{sub 2}O{sub 4} and MnFe{sub 2}O{sub 4} respectively, whereas the samples of NiFe{sub 2}O{sub 4} and ZnFe{sub 2}O{sub 4} show a superparamagnetic behavior. Highlights: ► Nanocrystalline MFe{sub 2}O{sub 4} powders were synthesized by a novel hydrothermal method. ► Metal acetylacetonates and aloe vera plant-extracted solution are used. ► This biosynthetic route is very simple and provides high-yield oxide nanomaterials. ► XRD and TEM results indicate that the prepared samples have only spinel structure. ► The maximum M{sub s} of 68.9 emu/g at 10 kOe were observed for the samples of MnFe{sub 2}O{sub 4}. - Abstract: Nanocrystalline spinel ferrite MFe{sub 2}O{sub 4} (M = Ni, Co, Mn, Mg, Zn) powders were synthesized by a novel hydrothermal method using Fe(acac){sub 3}, M(acac){sub 3} (M = Ni, Co, Mn, Mg, Zn) and aloe vera plant extracted solution. The X-ray diffraction and selected-area electron diffraction results indicate that the synthesized nanocrystalline have only spinel structure without the presence of other phase impurities. The crystal structure and morphology of the spinel ferrite powders, as revealed by TEM, show that the NiFe{sub 2}O{sub 4} and CoFe{sub 2}O{sub 4} samples contain nanoparticles, whereas the MnFe{sub 2}O{sub 4} and MgFe{sub 2}O{sub 4} samples consist of many nanoplatelets and nanoparticles. Interestingly, the ZnFe{sub 2}O{sub 4} sample contains plate-like structure of networked nanocrystalline particles. Room temperature magnetization results show a ferromagnetic behavior of the CoFe{sub 2}O{sub 4}, MnFe{sub 2}O{sub 4} and MgFe{sub 2}O{sub 4} samples, whereas the

  7. Photoactivation of the Ni-SIr state to the Ni-SIa state in [NiFe] hydrogenase: FT-IR study on the light reactivity of the ready Ni-SIr state and as-isolated enzyme revisited.

    PubMed

    Tai, Hulin; Xu, Liyang; Inoue, Seiya; Nishikawa, Koji; Higuchi, Yoshiki; Hirota, Shun

    2016-08-10

    The Ni-SIr state of [NiFe] hydrogenase from Desulfovibrio vulgaris Miyazaki F was photoactivated to its Ni-SIa state by Ar(+) laser irradiation at 514.5 nm, whereas the Ni-SL state was light induced from a newly identified state, which was less active than any other identified state and existed in the "as-isolated" enzyme.

  8. Size-controlled synthesis of NiFe2O4 nanospheres via a PEG assisted hydrothermal route and their catalytic properties in oxidation of alcohols by periodic acid

    NASA Astrophysics Data System (ADS)

    Paul, Bappi; Purkayastha, Debraj Dhar; Dhar, Siddhartha Sankar

    2016-05-01

    A novel and facile approach for synthesis of spinel nickel ferrites (NiFe2O4) nanoparticles (NPs) employing homogeneous chemical precipitation followed by hydrothermal heating is reported. The synthesis involves use of tributylamine (TBA) as a hydroxylating agent in synthesis of nickel ferrites. Polyethylene glycol (PEG) 4000 was used as surfactant. As-synthesized NiFe2O4 NPs were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption-desorption isotherm (BET) and vibrating sample magnetometry (VSM). The XRD pattern revealed formation of cubic face-centered NiFe2O4 and TEM image showed spherical particles of sizes 2-10 nm. These NiFe2O4 NPs were used as magnetically recoverable catalyst in oxidation of cyclic alcohols to their corresponding aldehydes by periodic acid. This eco-friendly procedure affords products in very high yield and selectivity. The reusability of the catalyst is proved to be noteworthy as the material exhibits no significant changes in its catalytic activity even after five cycles of reuse.

  9. Transcriptional regulation of genes encoding the selenium-free [NiFe]-hydrogenases in the archaeon Methanococcus voltae involves positive and negative control elements.

    PubMed Central

    Noll, I; Müller, S; Klein, A

    1999-01-01

    Methanococcus voltae harbors genetic information for two pairs of homologous [NiFe]-hydrogenases. Two of the enzymes contain selenocysteine, while the other two gene groups encode apparent isoenzymes that carry cysteinyl residues in the homologous positions. The genes coding for the selenium-free enzymes, frc and vhc, are expressed only under selenium limitation. They are transcribed out of a common intergenic region. A series of deletions made in the intergenic region localized a common negative regulatory element for the vhc and frc promoters as well as two activator elements that are specific for each of the two transcription units. Repeated sequences, partially overlapping the frc promoter, were also detected. Mutations in these repeated heptanucleotide sequences led to a weak induction of a reporter gene under the control of the frc promoters in the presence of selenium. This result suggests that the heptamer repeats contribute to the negative regulation of the frc transcription unit. PMID:10430564

  10. Exchange bias of CoO1-δ/(NiFe,Fe) system with blocking temperature beyond Néel temperature of bulk CoO

    NASA Astrophysics Data System (ADS)

    Ding, S. L.; Wu, R.; Fu, J. B.; Wen, X.; Du, H. L.; Liu, S. Q.; Han, J. Z.; Yang, Y. C.; Wang, C. S.; Zhou, D.; Yang, J. B.

    2015-10-01

    The exchange bias effects in pulsed laser deposited CoO1-δ/(NiFe,Fe) bilayers were investigated. An anomalously high blocking temperature (TB) of 325 K was obtained for the as-deposited CoO1-δ/ferromagnet bilayers, which is 33 K higher than the Néel temperature of the bulk CoO (TN = 292 K). The amount of oxygen vacancies δ in the CoO1-δ film can be controlled by a post-annealing treatment in the O2 atmosphere. The TB of the CoO1-δ/ferromagnet bilayers increases with an increasing δ from δ = 0 to δ = 0.16. Our results indicate that the high TB of CoO1-δ/ferromagnet bilayers originates from the enhancement of the magnetic interaction in the CoO1-δ layer owing to O2- vacancies.

  11. Distinct magnetism in ultrathin epitaxial NiFe2O4 films on MgAl2O4 and SrTiO3 single crystalline substrates

    NASA Astrophysics Data System (ADS)

    Foerster, Michael; Rebled, José Manuel; Estradé, Sònia; Sánchez, Florencio; Peiró, Francesca; Fontcuberta, Josep

    2011-10-01

    Spinel ferrites are being considered for advanced spintronic applications. Here, we report on the magnetic properties of ultrathin (3-37 nm) epitaxial films of NiFe2O4 (NFO) on MgAl2O4 (MAO) and SrTiO3 (STO) single crystalline substrates. It is found that NFO films on STO display superparamagnetic response down to 50 K, whereas films grown on MAO display ferrimagnetic response up to room temperature. Microstructural information indicates that this distinct response can be attributed to the different growth mechanisms of the spinel ferrite on the isostructural MAO substrate (two-dimensional growth) and the perovskite STO (Volmer-Weber three-dimensional growth). We discuss the reasons for this distinct behavior and its relevance for the integration of ferrites in epitaxial heterostructures for tunnel devices.

  12. Physical characteristics and cation distribution of NiFe2O4 thin films with high resistivity prepared by reactive co-sputtering

    NASA Astrophysics Data System (ADS)

    Klewe, C.; Meinert, M.; Boehnke, A.; Kuepper, K.; Arenholz, E.; Gupta, A.; Schmalhorst, J.-M.; Kuschel, T.; Reiss, G.

    2014-03-01

    We fabricated NiFe2O4 thin films on MgAl2O4 (001) substrates by reactive dc magnetron co-sputtering in a pure oxygen atmosphere at different substrate temperatures. The film properties were investigated by various techniques with a focus on their structure, surface topography, magnetic characteristics, and transport properties. Structural analysis revealed a good crystallization with epitaxial growth and low roughness and a similar quality as in films grown by pulsed laser deposition. Electrical conductivity measurements showed high room temperature resistivity (12 Ω m), but low activation energy, indicating an extrinsic transport mechanism. A band gap of about 1.55 eV was found by optical spectroscopy. Detailed x-ray spectroscopy studies confirmed the samples to be ferrimagnetic with fully compensated Fe moments. By comparison with multiplet calculations of the spectra, we found that the cation valencies are to a large extent Ni2+ and Fe3+.

  13. Direct comparison of the performance of a bio-inspired synthetic nickel catalyst and a [NiFe]-hydrogenase, both covalently attached to electrodes.

    PubMed

    Rodriguez-Maciá, Patricia; Dutta, Arnab; Lubitz, Wolfgang; Shaw, Wendy J; Rüdiger, Olaf

    2015-10-12

    The active site of hydrogenases has been a source of inspiration for the development of molecular catalysts. However, direct comparisons between molecular catalysts and enzymes have not been possible because different techniques are used to evaluate both types of catalysts, minimizing our ability to determine how far we have come in mimicking the enzymatic performance. The catalytic properties of the [Ni(P(Cy) 2 N(Gly) 2 )2 ](2+) complex with the [NiFe]-hydrogenase from Desulfovibrio vulgaris immobilized on a functionalized electrode were compared under identical conditions. At pH 7, the enzyme shows higher activity and lower overpotential with better stability, while at low pH, the molecular catalyst outperforms the enzyme in all respects. This is the first direct comparison of enzymes and molecular complexes, enabling a unique understanding of the benefits and detriments of both systems, and advancing our understanding of the utilization of these bio-inspired complexes in fuel cells.

  14. Weakened Flexural Strength of Nanocrystalline Nanoporous Gold by Grain Refinement.

    PubMed

    Gwak, Eun-Ji; Kim, Ju-Young

    2016-04-13

    High density of grain boundaries in solid materials generally leads to high strength because grain boundaries act as strong obstacles to dislocation activity. We find that the flexural strength of nanoporous gold of grain size 206 nm is 33.6% lower than that of grain size 238 μm. We prepared three gold-silver precursor alloys, well-annealed, prestrained, and high-energy ball-milled, from which nanoporous gold samples were obtained by the same free-corrosion dealloying process. Ligaments of the same size are formed regardless of precursor alloys, and microstructural aspects of precursor alloys such as crystallographic orientation and grain size is preserved in the dealloying process. While the nanoindentation hardness of three nanoporous golds is independent of microstructural variation, flexural strength of nanocrystalline nanoporous gold is significantly lower than that of nanoporous golds with much larger grain size. We investigate weakening mechanisms of grain boundaries in nanocrystalline nanoporous gold, leading to weakening of flexural strength.

  15. Weakened Flexural Strength of Nanocrystalline Nanoporous Gold by Grain Refinement.

    PubMed

    Gwak, Eun-Ji; Kim, Ju-Young

    2016-04-13

    High density of grain boundaries in solid materials generally leads to high strength because grain boundaries act as strong obstacles to dislocation activity. We find that the flexural strength of nanoporous gold of grain size 206 nm is 33.6% lower than that of grain size 238 μm. We prepared three gold-silver precursor alloys, well-annealed, prestrained, and high-energy ball-milled, from which nanoporous gold samples were obtained by the same free-corrosion dealloying process. Ligaments of the same size are formed regardless of precursor alloys, and microstructural aspects of precursor alloys such as crystallographic orientation and grain size is preserved in the dealloying process. While the nanoindentation hardness of three nanoporous golds is independent of microstructural variation, flexural strength of nanocrystalline nanoporous gold is significantly lower than that of nanoporous golds with much larger grain size. We investigate weakening mechanisms of grain boundaries in nanocrystalline nanoporous gold, leading to weakening of flexural strength. PMID:26982460

  16. Novel [NiFe]- and [FeFe]-hydrogenase gene transcripts indicative of active facultative aerobes and obligate anaerobes in earthworm gut contents.

    PubMed

    Schmidt, Oliver; Wüst, Pia K; Hellmuth, Susanne; Borst, Katharina; Horn, Marcus A; Drake, Harold L

    2011-09-01

    The concomitant occurrence of molecular hydrogen (H(2)) and organic acids along the alimentary canal of the earthworm is indicative of ongoing fermentation during gut passage. Fermentative H(2) production is catalyzed by [FeFe]-hydrogenases and group 4 [NiFe]-hydrogenases in obligate anaerobes (e.g., Clostridiales) and facultative aerobes (e.g., Enterobacteriaceae), respectively, functional groups that might respond differently to contrasting redox conditions. Thus, the objectives of this study were to assess the redox potentials of the alimentary canal of Lumbricus terrestris and analyze the hydrogenase transcript diversities of H(2) producers in glucose-supplemented gut content microcosms. Although redox potentials in the core of the alimentary canal were variable on an individual worm basis, average redox potentials were similar. The lowest redox potentials occurred in the foregut and midgut regions, averaging 40 and 110 mV, respectively. Correlation plots between hydrogenase amino acid sequences and 16S rRNA gene sequences indicated that closely related hydrogenases belonged to closely related taxa, whereas distantly related hydrogenases did not necessarily belong to distantly related taxa. Of 178 [FeFe]-hydrogenase gene transcripts, 177 clustered in 12 Clostridiales-affiliated operational taxonomic units, the majority of which were indicative of heretofore unknown hydrogenases. Of 86 group 4 [NiFe]-hydrogenase gene transcripts, 79% and 21% were affiliated with organisms in the Enterobacteriaceae and Aeromonadaceae, respectively. The collective results (i) suggest that fermenters must cope with variable and moderately oxidative redox conditions along the alimentary canal, (ii) demonstrate that heretofore undetected hydrogenases are present in the earthworm gut, and (iii) corroborate previous findings implicating Clostridiaceae and Enterobacteriaceae as active fermentative taxa in earthworm gut content. PMID:21784904

  17. Structural basis for a [4Fe-3S] cluster in the oxygen-tolerant membrane-bound [NiFe]-hydrogenase.

    PubMed

    Shomura, Yasuhito; Yoon, Ki-Seok; Nishihara, Hirofumi; Higuchi, Yoshiki

    2011-11-10

    Membrane-bound respiratory [NiFe]-hydrogenase (MBH), a H(2)-uptake enzyme found in the periplasmic space of bacteria, catalyses the oxidation of dihydrogen: H(2) → 2H(+) + 2e(-) (ref. 1). In contrast to the well-studied O(2)-sensitive [NiFe]-hydrogenases (referred to as the standard enzymes), MBH has an O(2)-tolerant H(2) oxidation activity; however, the mechanism of O(2) tolerance is unclear. Here we report the crystal structures of Hydrogenovibrio marinus MBH in three different redox conditions at resolutions between 1.18 and 1.32 Å. We find that the proximal iron-sulphur (Fe-S) cluster of MBH has a [4Fe-3S] structure coordinated by six cysteine residues--in contrast to the [4Fe-4S] cubane structure coordinated by four cysteine residues found in the proximal Fe-S cluster of the standard enzymes--and that an amide nitrogen of the polypeptide backbone is deprotonated and additionally coordinates the cluster when chemically oxidized, thus stabilizing the superoxidized state of the cluster. The structure of MBH is very similar to that of the O(2)-sensitive standard enzymes except for the proximal Fe-S cluster. Our results give a reasonable explanation why the O(2) tolerance of MBH is attributable to the unique proximal Fe-S cluster; we propose that the cluster is not only a component of the electron transfer for the catalytic cycle, but that it also donates two electrons and one proton crucial for the appropriate reduction of O(2) in preventing the formation of an unready, inactive state of the enzyme. PMID:22002607

  18. Relationship between Ni(II) and Zn(II) Coordination and Nucleotide Binding by the Helicobacter pylori [NiFe]-Hydrogenase and Urease Maturation Factor HypB*

    PubMed Central

    Sydor, Andrew M.; Lebrette, Hugo; Ariyakumaran, Rishikesh; Cavazza, Christine; Zamble, Deborah B.

    2014-01-01

    The pathogen Helicobacter pylori requires two nickel-containing enzymes, urease and [NiFe]-hydrogenase, for efficient colonization of the human gastric mucosa. These enzymes possess complex metallocenters that are assembled by teams of proteins in multistep pathways. One essential accessory protein is the GTPase HypB, which is required for Ni(II) delivery to [NiFe]-hydrogenase and participates in urease maturation. Ni(II) or Zn(II) binding to a site embedded in the GTPase domain of HypB modulates the enzymatic activity, suggesting a mechanism of regulation. In this study, biochemical and structural analyses of H. pylori HypB (HpHypB) revealed an intricate link between nucleotide and metal binding. HpHypB nickel coordination, stoichiometry, and affinity were modulated by GTP and GDP, an effect not observed for zinc, and biochemical evidence suggests that His-107 coordination to nickel toggles on and off in a nucleotide-dependent manner. These results are consistent with the crystal structure of HpHypB loaded with Ni(II), GDP, and Pi, which reveals a nickel site distinct from that of zinc-loaded Methanocaldococcus jannaschii HypB as well as subtle changes to the protein structure. Furthermore, Cys-142, a metal ligand from the Switch II GTPase motif, was identified as a key component of the signal transduction between metal binding and the enzymatic activity. Finally, potassium accelerated the enzymatic activity of HpHypB but had no effect on the other biochemical properties of the protein. Altogether, this molecular level information about HpHypB provides insight into its cellular function and illuminates a possible mechanism of metal ion discrimination. PMID:24338018

  19. HupO, a Novel Regulator Involved in Thiosulfate-Responsive Control of HupSL [NiFe]-Hydrogenase Synthesis in Thiocapsa roseopersicina

    PubMed Central

    Nagy, Ildikó K.; Kovács, Kornél L.

    2016-01-01

    [NiFe]-hydrogenases are regulated by various factors to fulfill their physiological functions in bacterial cells. The photosynthetic purple sulfur bacterium Thiocapsa roseopersicina harbors four functional [NiFe]-hydrogenases: HynSL, HupSL, Hox1, and Hox2. Most of these hydrogenases are functionally linked to sulfur metabolism, and thiosulfate has a central role in this organism. The membrane-associated Hup hydrogenases have been shown to play a role in energy conservation through hydrogen recycling. The expression of Hup-type hydrogenases is regulated by H2 in Rhodobacter capsulatus and Cupriavidus necator; however, it has been shown that the corresponding hydrogen-sensing system is nonfunctional in T. roseopersicina and that thiosulfate is a regulating factor of hup expression. Here, we describe the discovery and analysis of mutants of a putative regulator (HupO) of the Hup hydrogenase in T. roseopersicina. HupO appears to mediate the transcriptional repression of Hup enzyme synthesis under low-thiosulfate conditions. We also demonstrate that the presence of the Hox1 hydrogenase strongly influences Hup enzyme synthesis in that hup expression was decreased significantly in the hox1 mutant. This reduction in Hup synthesis could be reversed by mutation of hupO, which resulted in strongly elevated hup expression, as well as Hup protein levels, and concomitant in vivo hydrogen uptake activity in the hox1 mutant. However, this regulatory control was observed only at low thiosulfate concentrations. Additionally, weak hydrogen-dependent hup expression was shown in the hupO mutant strain lacking the Hox1 hydrogenase. HupO-mediated Hup regulation therefore appears to link thiosulfate metabolism and the hydrogenase network in T. roseopersicina. PMID:26801573

  20. Structure of [NiFe] Hydrogenase Maturation Protein HypE from Escherichia coli and its Interaction with HypF

    SciTech Connect

    Rangarajan,E.; Asinas, A.; Proteau, A.; Munger, C.; Baardsnes, j.; Iannuzzi, P.; Matte, A.; Cygler, m.

    2008-01-01

    Hydrogenases are enzymes involved in hydrogen metabolism, utilizing H2 as an electron source. [NiFe] hydrogenases are heterodimeric Fe-S proteins, with a large subunit containing the reaction center involving Fe and Ni metal ions and a small subunit containing one or more Fe-S clusters. Maturation of the [NiFe] hydrogenase involves assembly of nonproteinaceous ligands on the large subunit by accessory proteins encoded by the hyp operon. HypE is an essential accessory protein and participates in the synthesis of two cyano groups found in the large subunit. We report the crystal structure of Escherichia coli HypE at 2.0- Angstroms resolution. HypE exhibits a fold similar to that of PurM and ThiL and forms dimers. The C-terminal catalytically essential Cys336 is internalized at the dimer interface between the N- and C-terminal domains. A mechanism for dehydration of the thiocarbamate to the thiocyanate is proposed, involving Asp83 and Glu272. The interactions of HypE and HypF were characterized in detail by surface plasmon resonance and isothermal titration calorimetry, revealing a Kd (dissociation constant) of {approx}400 nM. The stoichiometry and molecular weights of the complex were verified by size exclusion chromatography and gel scanning densitometry. These experiments reveal that HypE and HypF associate to form a stoichiometric, hetero-oligomeric complex predominantly consisting of a [EF]2 heterotetramer which exists in a dynamic equilibrium with the EF heterodimer. The surface plasmon resonance results indicate that a conformational change occurs upon heterodimerization which facilitates formation of a productive complex as part of the carbamate transfer reaction.

  1. Novel [NiFe]- and [FeFe]-Hydrogenase Gene Transcripts Indicative of Active Facultative Aerobes and Obligate Anaerobes in Earthworm Gut Contents▿†

    PubMed Central

    Schmidt, Oliver; Wüst, Pia K.; Hellmuth, Susanne; Borst, Katharina; Horn, Marcus A.; Drake, Harold L.

    2011-01-01

    The concomitant occurrence of molecular hydrogen (H2) and organic acids along the alimentary canal of the earthworm is indicative of ongoing fermentation during gut passage. Fermentative H2 production is catalyzed by [FeFe]-hydrogenases and group 4 [NiFe]-hydrogenases in obligate anaerobes (e.g., Clostridiales) and facultative aerobes (e.g., Enterobacteriaceae), respectively, functional groups that might respond differently to contrasting redox conditions. Thus, the objectives of this study were to assess the redox potentials of the alimentary canal of Lumbricus terrestris and analyze the hydrogenase transcript diversities of H2 producers in glucose-supplemented gut content microcosms. Although redox potentials in the core of the alimentary canal were variable on an individual worm basis, average redox potentials were similar. The lowest redox potentials occurred in the foregut and midgut regions, averaging 40 and 110 mV, respectively. Correlation plots between hydrogenase amino acid sequences and 16S rRNA gene sequences indicated that closely related hydrogenases belonged to closely related taxa, whereas distantly related hydrogenases did not necessarily belong to distantly related taxa. Of 178 [FeFe]-hydrogenase gene transcripts, 177 clustered in 12 Clostridiales-affiliated operational taxonomic units, the majority of which were indicative of heretofore unknown hydrogenases. Of 86 group 4 [NiFe]-hydrogenase gene transcripts, 79% and 21% were affiliated with organisms in the Enterobacteriaceae and Aeromonadaceae, respectively. The collective results (i) suggest that fermenters must cope with variable and moderately oxidative redox conditions along the alimentary canal, (ii) demonstrate that heretofore undetected hydrogenases are present in the earthworm gut, and (iii) corroborate previous findings implicating Clostridiaceae and Enterobacteriaceae as active fermentative taxa in earthworm gut content. PMID:21784904

  2. Magnetization Reversal Processes, in the Nanocrystalline Fe-Co-Zr-Ti-Pr-B Magnets

    NASA Astrophysics Data System (ADS)

    Pawlik, K.; Pawlik, P.; Wysłocki, J. J.; Kaszuwara, W.

    2008-01-01

    Magnetization reversal processes in the magnets derived from the Fe60Co13Zr1Ti3Pr9B14 alloy were investigated. It was shown that the processing technique affects the magnetization reversal processes. For the nanocrystalline ribbon samples pinning of the domain walls arises at low external magnetic fields while nucleation of reversed domains occurs at higher fields. However, the nucleation fields are lower than the pinning fields for the nanocrystalline rod and tube samples produced by suction-casting technique.

  3. Materials Properties Database for Selection of High-Temperature Alloys and Concepts of Alloy Design for SOFC Applications

    SciTech Connect

    Yang, Z Gary; Paxton, Dean M.; Weil, K. Scott; Stevenson, Jeffry W.; Singh, Prabhakar

    2002-11-24

    To serve as an interconnect / gas separator in an SOFC stack, an alloy should demonstrate the ability to provide (i) bulk and surface stability against oxidation and corrosion during prolonged exposure to the fuel cell environment, (ii) thermal expansion compatibility with the other stack components, (iii) chemical compatibility with adjacent stack components, (iv) high electrical conductivity of the surface reaction products, (v) mechanical reliability and durability at cell exposure conditions, (vii) good manufacturability, processability and fabricability, and (viii) cost effectiveness. As the first step of this approach, a composition and property database was compiled for high temperature alloys in order to assist in determining which alloys offer the most promise for SOFC interconnect applications in terms of oxidation and corrosion resistance. The high temperature alloys of interest included Ni-, Fe-, Co-base superal

  4. [NiFe] hydrogenase from Desulfovibrio desulfuricans ATCC 27774: gene sequencing, three-dimensional structure determination and refinement at 1.8 A and modelling studies of its interaction with the tetrahaem cytochrome c3.

    PubMed

    Matias, P M; Soares, C M; Saraiva, L M; Coelho, R; Morais, J; Le Gall, J; Carrondo, M A

    2001-01-01

    The primary and three-dimensional structures of a [NiFe] hydrogenase isolated from D. desulfitricans ATCC 27774 were determined, by nucleotide analysis and single-crystal X-ray crystallography. The three-dimensional structural model was refined to R=0.167 and Rfree=0.223 using data to 1.8 A resolution. Two unique structural features are observed: the [4Fe-4S] cluster nearest the [NiFe] centre has been modified [4Fe-3S-3O] by loss of one sulfur atom and inclusion of three oxygen atoms; a three-fold disorder was observed for Cys536 which binds to the nickel atom in the [NiFe] centre. Also, the bridging sulfur atom that caps the active site was found to have partial occupancy, thus corresponding to a partly activated enzyme. These structural features may have biological relevance. In particular, the two less-populated rotamers of Cys536 may be involved in the activation process of the enzyme, as well as in the catalytic cycle. Molecular modelling studies were carried out on the interaction between this [NiFe] hydrogenase and its physiological partner, the tetrahaem cytochrome c3 from the same organism. The lowest energy docking solutions were found to correspond to an interaction between the haem IV region in tetrahaem cytochrome c3 with the distal [4Fe-4S] cluster in [NiFe] hydrogenase. This interaction should correspond to efficient electron transfer and be physiologically relevant, given the proximity of the two redox centres and the fact that electron transfer decay coupling calculations show high coupling values and a short electron transfer pathway. On the other hand, other docking solutions have been found that, despite showing low electron transfer efficiency, may give clues on possible proton transfer mechanisms between the two molecules. PMID:11191224

  5. Structural and Magnetic Analysis of Nanocrystalline Lead Europium Sulfide (PbxEuyS)

    SciTech Connect

    Somarajan, Suseela; Harrison, Melissa A; Koktysh, Dmitry S.; He, Weidong; Stillwell, Ryan L; Harl, Bobby; Schmidt, Ben; Rogers, Bridget; Payzant, E Andrew; Dickerson, II, James H.

    2012-01-01

    The authors report the synthesis of nanocrystalline, alloyed PbEuS, a potentially important dilute magnetic semiconductor. The thermolysis of mixed precursors has been adapted for the formation of homogeneous alloyed nanocrystals. X-ray diffraction and magnetization measurements of ternary PbEuS nanocrystals provide convincing evidence that no phase separation occurs in these nanomaterials for europium concentrations up to x = 0.17. X-ray photoelectron spectroscopy provides the atomic composition for PbEuS alloy nanocrystals juxtaposed with the ratio of the starting precursors.

  6. Redox controls on Ni-Fe-PGE mineralization and Re/Os fractionation during serpentinization of abyssal peridotite

    NASA Astrophysics Data System (ADS)

    Foustoukos, Dionysis I.; Bizimis, Michael; Frisby, Carl; Shirey, Steven B.

    2015-02-01

    Awaruite (Ni2Fe to Ni3Fe) is often used to infer fugacity and redox gradients in hydrothermally altered peridotites. However, discrepant petrological and thermodynamic data suggest that the fO2-fS2 stability field of awaruite is not well constrained. In this study, we assess the thermodynamic properties of awaruite and re-evaluate the Fe-Ni-S systematics of hydrothermally altered peridotites. New experimental data indicate that awaruite is stable at higher fO2 than previously thought, supporting the common occurrence of awaruite in the reaction zone of modern and ancient ultramafic-hosted hydrothermal vent systems. Awaruite is known to catalyze the abiogenic synthesis of methane during active serpentinization, contributing to methanogenesis at modern oceanic hydrothermal systems and potentially on early Earth. The enhanced stability field of awaruite determined here suggests that abiogenic methanogenesis may be active at a broad range of redox conditions. Serpentinized peridotites also contain platinum-group element (PGE)-Re sulfides and metal alloys that can be derived from desulfurization of primary mantle sulfides under low fS2. Thermodynamic calculations suggest that Os will exist as metal and Re as ReS2 in the redox stability field of awaruite. Under a relatively broad range of fS2-fO2 conditions, hydrothermal alteration and desulfurization of primary mantle may produce open system behavior in the Re/Os system and variable Re-PGE ratios and contribute over time to the Os isotopic heterogeneity of the mantle, through subduction and recycling of altered oceanic lithosphere. PGE-metal alloys occur at such low abundances in peridotite that they often are nearly impossible to find. The stability of awaruite at higher fO2 suggests that it can coexist with Os-Ir-Pt metal alloys, making it an important indicator mineral for their presence in hydrothermally altered peridotites.

  7. Improve oxidation resistance at high temperature by nanocrystalline surface layer

    PubMed Central

    Xia, Z. X.; Zhang, C.; Huang, X. F.; Liu, W. B.; Yang, Z. G.

    2015-01-01

    An interesting change of scale sequence occurred during oxidation of nanocrystalline surface layer by means of a surface mechanical attrition treatment. The three-layer oxide structure from the surface towards the matrix is Fe3O4, spinel FeCr2O4 and corundum (Fe,Cr)2O3, which is different from the typical two-layer scale consisted of an Fe3O4 outer layer and an FeCr2O4 inner layer in conventional P91 steel. The diffusivity of Cr, Fe and O is enhanced concurrently in the nanocrystalline surface layer, which causes the fast oxidation in the initial oxidation stage. The formation of (Fe,Cr)2O3 inner layer would inhabit fast diffusion of alloy elements in the nanocrystalline surface layer of P91 steel in the later oxidation stage, and it causes a decrease in the parabolic oxidation rate compared with conventional specimens. This study provides a novel approach to improve the oxidation resistance of heat resistant steel without changing its Cr content. PMID:26269034

  8. The martensitic transformation and magnetic properties in Ni50- x Fe x Mn32Al18 ferromagnetic shape memory alloys

    NASA Astrophysics Data System (ADS)

    Xuan, H. C.; Zhang, Y. Q.; Li, H.; Han, P. D.; Wang, D. H.; Du, Y. W.

    2015-05-01

    The martensitic transformation (MT) and magnetic properties have been investigated in a series of Ni50- x Fe x Mn32Al18 ferromagnetic shape memory alloys. The substitution of Fe for Ni reduces the MT temperature of Ni-Fe-Mn-Al alloys effectively, and the magnetization of the austenite was significantly enhanced in these high-doped alloys. The Fe introduction converts antiferromagnetic austenite to ferrimagnetic state, and therefore, the unique MT occurs between ferrimagnetic and antiferromagnetic state in these alloys. The MT temperatures decreased by about 15 K under the magnetic field of 30 kOe for x = 8 alloy. The positive value of magnetic entropy change was determined to 3.35 J/kg K around the MT in the field change of 30 kOe for x = 6 alloy. These results suggest that Ni50- x Fe x Mn32Al18 alloys would be the promising candidates for magnetic multifunctional materials.

  9. NANOCRYSTALLINE GROWTH AND GRAIN-SIZE EFFECTS IN AU-CU ELECTRODEPOSITS

    SciTech Connect

    Jankowski, A F; Saw, C K; Harper, J F; Vallier, R F; Ferreira, J L; Hayes, J P

    2005-02-25

    The processing-structure-property relationship is investigated for electrodeposited foils of the gold-copper alloy system. A model is presented that relates the deposition process parameters to the nanocrystalline grain size. An activation energy of 1.52 eV {center_dot} atom{sup -1} for growth is determined for a long pulse (>10 msec) mode, and is 0.16 eV {center_dot} atom{sup -1} for short pulses (<5 msec). The affect of nanocrystalline grain size on the mechanical properties is assessed using indentation measurements. A Hall-Petch type variation of the Vickers microhardness with nanocrystalline grain size (>6 nm) is observed for Au-Cu samples with 1-12 wt.% Cu as tested in cross-section. The hardness increases three-fold from a rule-of-mixtures value <1 GPa to a maximum of 2.9 GPa.

  10. New atom probe approaches to studying segregation in nanocrystalline materials.

    PubMed

    Samudrala, S K; Felfer, P J; Araullo-Peters, V J; Cao, Y; Liao, X Z; Cairney, J M

    2013-09-01

    Atom probe is a technique that is highly suited to the study of nanocrystalline materials. It can provide accurate atomic-scale information about the composition of grain boundaries in three dimensions. In this paper we have analysed the microstructure of a nanocrystalline super-duplex stainless steel prepared by high pressure torsion (HPT). Not all of the grain boundaries in this alloy display obvious segregation, making visualisation of the microstructure challenging. In addition, the grain boundaries present in the atom probe data acquired from this alloy have complex shapes that are curved at the scale of the dataset and the interfacial excess varies considerably over the boundaries, making the accurate characterisation of the distribution of solute challenging using existing analysis techniques. In this paper we present two new data treatment methods that allow the visualisation of boundaries with little or no segregation, the delineation of boundaries for further analysis and the quantitative analysis of Gibbsian interfacial excess at boundaries, including the capability of excess mapping.

  11. Ion irradiation induced defect evolution in Ni and Ni-based FCC equiatomic binary alloys

    NASA Astrophysics Data System (ADS)

    Jin, K.; Bei, H.; Zhang, Y.

    2016-04-01

    In order to explore the chemical effects on radiation response of alloys with multi-principal elements, defect evolution under Au ion irradiation was investigated in the elemental Ni, equiatomic NiCo and NiFe alloys. Single crystals were successfully grown in an optical floating zone furnace and their (100) surfaces were irradiated with 3 MeV Au ions at fluences ranging from 1 × 1013 to 5 × 1015 ions cm-2 at room temperature. The irradiation-induced defect evolution was analyzed by using ion channeling technique. Experiment shows that NiFe is more irradiation-resistant than NiCo and pure Ni at low fluences. With continuously increasing the ion fluences, damage level is eventually saturated for all materials but at different dose levels. The saturation level in pure Ni appears at relatively lower irradiation fluence than the alloys, suggesting that damage accumulation slows down in the alloys. Under high-fluence irradiations, pure Ni has wider damage ranges than the alloys, indicating that defects in pure Ni have high mobility.

  12. Ion irradiation induced defect evolution in Ni and Ni-based FCC equiatomic binary alloys

    DOE PAGESBeta

    Jin, Ke; Zhang, Yanwen; Bei, Hongbin

    2016-01-01

    In order to explore the chemical effects on radiation response of alloys with multi-principal elements, defect evolution under Au ion irradiation was investigated in the elemental Ni, equiatomic NiCo and NiFe alloys. Single crystals were successfully grown in an optical floating zone furnace and their (100) surfaces were irradiated with 3 MeV Au ions at fluences ranging from 1 × 1013 to 5 × 1015 ions cm–2 at room temperature. The irradiation-induced defect evolution was analyzed by using ion channeling technique. Experiment shows that NiFe is more irradiation-resistant than NiCo and pure Ni at low fluences. With continuously increasing themore » ion fluences, damage level is eventually saturated for all materials but at different dose levels. The saturation level in pure Ni appears at relatively lower irradiation fluence than the alloys, suggesting that damage accumulation slows down in the alloys. Here, under high-fluence irradiations, pure Ni has wider damage ranges than the alloys, indicating that defects in pure Ni have high mobility.« less

  13. Ion irradiation induced defect evolution in Ni and Ni-based FCC equiatomic binary alloys

    SciTech Connect

    Jin, Ke; Zhang, Yanwen; Bei, Hongbin

    2016-01-01

    In order to explore the chemical effects on radiation response of alloys with multi-principal elements, defect evolution under Au ion irradiation was investigated in the elemental Ni, equiatomic NiCo and NiFe alloys. Single crystals were successfully grown in an optical floating zone furnace and their (100) surfaces were irradiated with 3 MeV Au ions at fluences ranging from 1 × 1013 to 5 × 1015 ions cm–2 at room temperature. The irradiation-induced defect evolution was analyzed by using ion channeling technique. Experiment shows that NiFe is more irradiation-resistant than NiCo and pure Ni at low fluences. With continuously increasing the ion fluences, damage level is eventually saturated for all materials but at different dose levels. The saturation level in pure Ni appears at relatively lower irradiation fluence than the alloys, suggesting that damage accumulation slows down in the alloys. Here, under high-fluence irradiations, pure Ni has wider damage ranges than the alloys, indicating that defects in pure Ni have high mobility.

  14. Magnetization dynamics in an exchange-coupled NiFe/CoFe bilayer studied by x-ray detected ferromagnetic resonance

    NASA Astrophysics Data System (ADS)

    Stenning, G. B. G.; Shelford, L. R.; Cavill, S. A.; Hoffmann, F.; Haertinger, M.; Hesjedal, T.; Woltersdorf, G.; Bowden, G. J.; Gregory, S. A.; Back, C. H.; de Groot, P. A. J.; van der Laan, G.

    2015-01-01

    Exchange-coupled hard and soft magnetic layers find extensive use in data storage applications, for which their dynamical response has great importance. With bulk techniques, such as ferromagnetic resonance (FMR), it is difficult to access the behaviour and precise influence of each individual layer. By contrast, the synchrotron radiation-based technique of x-ray detected ferromagnetic resonance (XFMR) allows element-specific and phase-resolved FMR measurements in the frequency range 0.5-11 GHz. Here, we report the study of the magnetization dynamics of an exchange-coupled Ni0.81Fe0.19 (43.5 nm)/Co0.5Fe0.5 (30 nm) bilayer system using magnetometry and vector network analyser FMR, combined with XFMR at the Ni and Co L2 x-ray absorption edges. The epitaxially grown bilayer exhibits two principal resonances denoted as the acoustic and optical modes. FMR experiments show that the Kittel curves of the two layers cannot be taken in isolation, but that their modelling needs to account for an interlayer exchange coupling. The angular dependence of FMR indicates a collective effect for the modes of the magnetically hard CoFe and soft NiFe layer. The XFMR precessional scans show that the acoustic mode is dominated by the Ni signal with the Co and Ni magnetization precessing in phase, whereas the optical mode is dominated by the Co signal with the Co and Ni magnetization precessing in anti-phase. The response of the Co signal at the Ni resonance, and vice versa, show induced changes in both amplitude and phase, which can be ascribed to the interface exchange coupling. An interesting aspect of phase-resolved XFMR is the ability to distinguish between static and dynamic exchange coupling. The element-specific precessional scans of the NiFe/CoFe bilayer clearly have the signature of static exchange coupling, in which the effective field in one layer is aligned along the magnetization direction of the other layer.

  15. Effect of alloying elements on the corrosion behaviour of copper-nickel alloys in a marine environment

    NASA Astrophysics Data System (ADS)

    Taher, Abulmaali M. Y.

    Copper-nickel alloys have been used in many applications in marine environments, because of excellent corrosion and biofouling resistance. In this study, the effect of alloying elements (including iron, aluminum, chromium, cobalt, titanium, molybdenum, indium, and vanadium) on the corrosion behaviour of 90 w% copper-10 w% nickel alloys in sea water are investigated. Experiments were performed at 298 K on a commercial copper-nickel alloy C70600 to serve as a reference point for the synthetic alloys. New copper-nickel alloys were prepared in an induction furnace, in an argon/7% vol. hydrogen atmosphere in cylindrical boron nitride crucibles. They were then homogenized at 950°C for 10 hours in the same protective atmosphere. The electrochemical behaviour was investigated by linear sweep voltammetry (LSV), cyclic polarization (CP), cyclic voltammetry (CV), Tafel extrapolation (TE) and electrochemical impedance spectroscopy (EIS). The corrosion product that formed on the surface was characterized using field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), electron probe microanalysis (EPMA), and wavelength dispersive spectroscopy (WDS). The electrochemical behaviour of commercial alloy C70600 depends on the amount of sulphate in the solution. Increasing the amount of sulphate to more than 400 ppm in the electrolyte limits the ability of the passive film to protect the alloy. The behaviour of the commercial alloy in sea water was similar to that in a 2260 ppm sulphate artificial saline solution but was not exactly the same. The passive film formed on the surface was uniform in thickness and consisted of more than one layer. The passive film consisted mainly of chlorides in solutions with no sulphate. The presence of sulphate in the corrosive solutions produces a passive layer containing mainly chlorides with some sulphides (FeS, NiS, and CuS). The electrochemical behaviour of the synthetic Cu-Ni-Fe alloys

  16. The effect of alloying nickel with iron on the supersonic ballistic stage of high energy displacement cascades

    DOE PAGESBeta

    Béland, Laurent Karim; Osetsky, Yuri N.; Stoller, Roger E.

    2016-06-23

    Previous experimental and theoretical studies suggest that the production of extended defect structures by collision cascades is inhibited in equiatomic NiFe, in comparison to pure Ni. It is also known that the production of such extend defect structures results from the formation of subcascades by high-energy recoils and their subsequent interaction. A detailed analysis of the ballistics of 40 keV cascades in Ni and NiFe is performed to identify the formation of such subcascades and to assess their spatial distribution. It is found that subcascades in Ni and NiFe are created with nearly identical energies and distributed similarly in space.more » This suggests that the differences in production of extended defect structures is not related to processes taking place in the ballistic phase of the collision cascade. Lastly, these results can be generalized to other, more chemically complex, concentrated alloys where the elements have similar atomic numbers, such as many high-entropy alloys.« less

  17. Low core losses and magnetic properties of Fe85-86Si1-2B8P4Cu1 nanocrystalline alloys with high B for power applications (invited)

    NASA Astrophysics Data System (ADS)

    Makino, Akihiro; Kubota, Takeshi; Yubuta, Kunio; Inoue, Akihisa; Urata, Akiri; Matsumoto, Hiroyuki; Yoshida, Shigeyoshi

    2011-04-01

    Recently, the energy crisis and the continued growth in electrical power generation strongly demand minimization of wasteful energy dissipation. Magnetic core loss (W) is the main source of energy dissipation in motors and transformers. This requires the development of soft magnetic materials with low coercivity (Hc) and high magnetic flux density (B). Fe-rich Fe85-86Si1-2B8P4Cu1 (at. %) alloy ribbons made from industrial raw materials (containing some impurities) with 6 mm in width have a heteroamorphous structure containing a large number of extremely small Fe grains (less than 3 nm), resulting from the unique effects of P and Cu addition in proper amounts. Crystallization of these alloys by annealing shows a uniform precipitation of α-Fe, leading to a uniform nanocrystallized structure of α-Fe grains, 16-19 nm in size, accompanied by an intergranular amorphous layer about 1 nm in width. The wide ribbons exhibit high B of 1.82-1.85 T (at 800 A/m), almost comparable to commercial oriented Fe-3 mass% Si alloys. Excellent magnetic softness (low Hc of 2.6-5.8 A/m, high permeability of 2.4-2.7 × 104 at 1 kHz and small saturation magnetostriction of 2.3-2.4 × 10-6) along with high electrical resistivity (0.67-0.74 μΩ m) of these alloys result in superior frequency characteristics of core losses and a much lower W at 50 Hz up to the maximum induction of 1.75 T, in comparison to the silicon steels now in practical use for power applications.

  18. Photoactivation of the Ni-SIr state to the Ni-SIa state in [NiFe] hydrogenase: FT-IR study on the light reactivity of the ready Ni-SIr state and as-isolated enzyme revisited.

    PubMed

    Tai, Hulin; Xu, Liyang; Inoue, Seiya; Nishikawa, Koji; Higuchi, Yoshiki; Hirota, Shun

    2016-08-10

    The Ni-SIr state of [NiFe] hydrogenase from Desulfovibrio vulgaris Miyazaki F was photoactivated to its Ni-SIa state by Ar(+) laser irradiation at 514.5 nm, whereas the Ni-SL state was light induced from a newly identified state, which was less active than any other identified state and existed in the "as-isolated" enzyme. PMID:27456760

  19. Effects of annealing temperature variation on the evolution of structural and magnetic properties of NiFe2O4 nanoparticles synthesized by starch-assisted sol-gel auto-combustion method

    NASA Astrophysics Data System (ADS)

    Singh Yadav, Raghvendra; Havlica, Jaromir; Masilko, Jiri; Kalina, Lukas; Wasserbauer, Jaromir; Hajdúchová, Miroslava; Enev, Vojtěch; Kuřitka, Ivo; Kožáková, Zuzana

    2015-11-01

    Evolution of the structural and magnetic properties of NiFe2O4 nanoparticles synthesized by starch-assisted sol-gel auto-combustion method, and exposed to further annealing at 200 °C, 400 °C, 600 °C, 800 °C and 1000 °C, was evaluated in detail and correlation of these properties explored. The ferrite nanoparticles were characterized by X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy, Raman Spectroscopy, Fourier Transform Infrared Spectroscopy, X-ray Photoelectron Spectroscopy and Vibrating Sample Magnetometer. The X-ray diffraction patterns demonstrated single phase formation of NiFe2O4 spinel ferrite nanoparticles at different annealing temperature 200 °C, 400 °C, 600 °C, 800 °C and 1000 °C. The change in crystallite size with increase of annealing temperature is observed. The FE-SEM analysis also indicated an increase of particle size with increase of higher annealing temperature. The change in Raman modes and infrared absorption bands were noticed with change of particle size. The X-ray photoelectron spectroscopy revealed the presence of Ni2+ and Fe3+ at octahedral and tetrahedral sites in NiFe2O4 nanoparticles. The representative sample NiFe2O4 nanoparticles annealed at 400 °C, have mixed cation distribution (Ni0.23+2 Fe0.52+3)[ Ni0.77+2 Fe1.48+3 ]O4. The highest value of coercivity 62.35 Oe and saturation magnetization 34.10 erg/g were obtained at annealing temperature 600 °C and 1000 °C, respectively.

  20. The stress, surface spin and dipolar interaction in the diluted NiFe{sub 2}O{sub 4} nanoparticles by the SiO{sub 2} matrix: Characterization and analyses

    SciTech Connect

    Sun, X.; Ma, Y.Q. Xu, S.T.; Xu, Y.F.; Geng, B.Q.

    2015-09-15

    Well-dispersed uniform NiFe{sub 2}O{sub 4} nanoparticles (NPs) with an average particle size of 15.4 nm were synthesized by thermal decomposition of a metal–organic salt, and then were diluted in a SiO{sub 2} matrix via a sol–gel method with different concentration. The magnetization (M) dependence of NiFe{sub 2}O{sub 4}/SiO{sub 2} on the temperature (T) and on the applied magnetic field (H) was systematically characterized by the Quantum Design superconducting quantum interference device (SQUID) PPMS system. The results of M ~ H/T divide the magnetic properties between 10 K and 300 K into two regions: the low temperature blocked-particle regime below the blocking temperature T{sub B} and the interacting superparamagnetic (ISP) regime above T{sub B}. In the ISP regime, all samples deviate from the ideal Langevin superparamagnetic behavior due to the effective anisotropy induced by the stress, surface spins and interparticle dipolar interaction. The Raman spectra indicate that the stress in all samples exhibits the vibration behavior, which leads to the effective anisotropy and hence coercivity vibration. - Graphical abstract: Display Omitted - Highlights: • Increase of NiFe{sub 2}O{sub 4} NPs' concentration elevates T{sub B} and broadens ZFC peak. • NiFe{sub 2}O{sub 4}/SiO{sub 2} samples do not exhibit the ideal superparamagnetism above T{sub B}. • Stress leads to the effective anisotropy and hence H{sub c} vibration. • Stress vibration was characterized in detail by the Raman spectra.

  1. Voltammetric behavior of dopamine at a glassy carbon electrode modified with NiFe(2)O(4) magnetic nanoparticles decorated with multiwall carbon nanotubes.

    PubMed

    Ensafi, Ali A; Arashpour, B; Rezaei, B; Allafchian, Ali R

    2014-06-01

    Voltammetric behavior of dopamine was studied on a glassy carbon electrode (GCE) modified-NiFe(2)O(4) magnetic nanoparticles decorated with multiwall carbon nanotubes. Impedance spectroscopy and cyclic voltammetry were used to characterize the behavior of dopamine at the surface of modified-GCE. The modified electrode showed a synergic effect toward the oxidation of dopamine. The oxidation peak current is increased linearly with the dopamine concentration (at pH7.0) in wide dynamic ranges of 0.05-6.0 and 6.0-100μmolL(-1) with a detection limit of 0.02μmolL(-1), using differential pulse voltammetry. The selectivity of the method was studied and the results showed that the modified electrode is free from interference of organic compounds especially ascorbic acid, uric acid, cysteine and urea. Its applicability in the determination of dopamine in pharmaceutical, urine samples and human blood serum was also evaluated. The proposed electrochemical sensor has appropriate properties such as high selectivity, low detection limit and wide linear dynamic range when compared with that of the previous reported papers for dopamine detection.

  2. Discovery of Fe-Ce Oxide/BiVO4 Photoanodes through Combinatorial Exploration of Ni-Fe-Co-Ce Oxide Coatings.

    PubMed

    Shinde, Aniketa; Guevarra, Dan; Liu, Guiji; Sharp, Ian D; Toma, Francesca M; Gregoire, John M; Haber, Joel A

    2016-09-14

    An efficient photoanode is a prerequisite for a viable solar fuels technology. The challenges to realizing an efficient photoanode include the integration of a semiconductor light absorber and a metal oxide electrocatalyst to optimize corrosion protection, light trapping, hole transport, and photocarrier recombination sites. To efficiently explore metal oxide coatings, we employ a high-throughput methodology wherein a uniform BiVO4 film is coated with 858 unique metal oxide coatings covering a range of metal oxide loadings and the full (Ni-Fe-Co-Ce)Ox pseudoquaternary composition space. Photoelectrochemical characterization of the photoanodes reveals that specific combinations of metal oxide composition and loading provide up to a 13-fold increase in the maximum photoelectrochemical power generation for oxygen evolution in pH 13 electrolyte. Through mining of the high-throughput data we identify composition regions that form improved interfaces with BiVO4. Of particular note, integrated photoanodes with catalyst compositions in the range Fe(0.4-0.6)Ce(0.6-0.4)Ox exhibit high interface quality and excellent photoelectrochemical power conversion. Scaled-up inkjet-printed electrodes and photoanodic electrodeposition of this composition on BiVO4 confirms the discovery and the synthesis-independent interface improvement of (Fe-Ce)Ox coatings on BiVO4.

  3. Pulsed laser deposition of epitaxial YBa2Cu3O7-y / oxide multilayers onto textured NiFe substrates for coated conductor applications

    NASA Astrophysics Data System (ADS)

    Tomov, R. I.; Kursumovic, A.; Majoros, M.; Kang, D.-J.; Glowacki, B. A.; Evetts, J. E.

    2002-04-01

    Pulsed laser depositions of double-buffer and triple-buffer YBa2Cu3O7-y (YBCO)/Y2O3(YSZ)/CeO2 heterostructures have been performed in situ onto commercially available biaxially textured NiFe 50%/50% tape. The deposition in the forming gas (4% H2/Ar) from a CeO2 target and the deposition in vacuum from a CeO2:Pd composite target have been explored as two possible routes for cube-on-cube growth of the first buffer layer. The influence of the critical processing parameters on the texture is investigated and some of the issues involved in the reduction of NiO (111) and the formation of cube-on-cube NiO (200) growth are discussed. X-ray diffraction has been used for texture evaluation of the substrate and subsequent deposited layers. The substrate-buffer interface region has been studied by focused ion beam cross section electron microscopy. Both the buffers and YBCO layers show biaxial alignment with ω and φ scans having optimum YBCO full width at half maximum (FWHM) values of 4.3° and 8.8°, respectively. The morphology has been characterized using atomic force microscopy and scanning electron microscopy. The value of Tc (onset) has been measured at 90 K (ΔTc = 10 K). The critical current density, Jc, has been measured by transport measurements and magnetic measurements performed in a dc SQUID magnetometer.

  4. H₂-dependent azoreduction by Shewanella oneidensis MR-1: involvement of secreted flavins and both [Ni-Fe] and [Fe-Fe] hydrogenases.

    PubMed

    Le Laz, Sébastien; Kpebe, Arlette; Lorquin, Jean; Brugna, Myriam; Rousset, Marc

    2014-03-01

    In this paper, the hydrogen (H2)-dependent discoloration of azo dye amaranth by Shewanella oneidensis MR-1 was investigated. Experiments with hydrogenase-deficient strains demonstrated that periplasmic [Ni-Fe] hydrogenase (HyaB) and periplasmic [Fe-Fe] hydrogenase (HydA) are both respiratory hydrogenases of dissimilatory azoreduction in S. oneidensis MR-1. These findings suggest that HyaB and HydA can function as uptake hydrogenases that couple the oxidation of H2 to the reduction of amaranth to sustain cellular growth. This constitutes to our knowledge the first report of the involvement of [Fe-Fe] hydrogenase in a bacterial azoreduction process. Assays with respiratory inhibitors indicated that a menaquinone pool and different cytochromes were involved in the azoreduction process. High-performance liquid chromatography analysis revealed that flavin mononucleotide and riboflavin were secreted in culture supernatant by S. oneidensis MR-1 under H2-dependent conditions with concentration of 1.4 and 2.4 μmol g protein(-1), respectively. These endogenous flavins were shown to significantly accelerate the reduction of amaranth at micromolar concentrations acting as electron shuttles between the cell surface and the extracellular azo dye. This work may facilitate a better understanding of the mechanisms of azoreduction by S. oneidensis MR-1 and may have practical applications for microbiological treatments of dye-polluted industrial effluents.

  5. Direct Comparison of the Performance of a Bio-inspired Synthetic Nickel Catalyst and a [NiFe]-Hydrogenase, Both Covalently Attached to Electrodes

    SciTech Connect

    Rodriguez-Macia, Patricia; Dutta, Arnab; Lubitz, Wolfgang; Shaw, Wendy J.; Rudiger, Olaf

    2015-10-12

    The active site of hydrogenases has been a source of inspiration for the development of molecular catalysts. However, direct comparisons between molecular catalysts and enzymes have not been possible because different techniques are used to evaluate both types of catalysts, minimizing our ability to determine how far we’ve come in mimicking the impressive enzymatic performance. Here we directly compare the catalytic properties of the [Ni(PCy2NGly2)2]2+ complex with the [NiFe]-hydrogenase from Desulfobivrio vulgaris Miyazaki F (DvMF) immobilized to a functionalized electrode under identical conditions. At pH=7, the enzyme has higher performance in both activity and overpotential, and is more stable, while at low pH, the molecular catalyst outperforms the enzyme in all respects. The Ni complex also has increased tolerance to CO. This is the first direct comparison of enzymes and molecular complexes, enabling a unique understanding of the benefits and detriments of both systems, and advancing our understanding of the utilization of these bioinspired complexes in fuel cells. AD and WJS acknowledge the Office of Science Early Career Research Program through the US Department of Energy (US DOE), Office of Science, Office of Basic Energy Sciences (BES), and Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the US DOE.

  6. Characterization of a unique [FeS] cluster in the electron transfer chain of the oxygen tolerant [NiFe] hydrogenase from Aquifex aeolicus.

    PubMed

    Pandelia, Maria-Eirini; Nitschke, Wolfgang; Infossi, Pascale; Giudici-Orticoni, Marie-Thérèse; Bill, Eckhard; Lubitz, Wolfgang

    2011-04-12

    Iron-sulfur clusters are versatile electron transfer cofactors, ubiquitous in metalloenzymes such as hydrogenases. In the oxygen-tolerant Hydrogenase I from Aquifex aeolicus such electron "wires" form a relay to a diheme cytb, an integral part of a respiration pathway for the reduction of O(2) to water. Amino acid sequence comparison with oxygen-sensitive hydrogenases showed conserved binding motifs for three iron-sulfur clusters, the nature and properties of which were unknown so far. Electron paramagnetic resonance spectra exhibited complex signals that disclose interesting features and spin-coupling patterns; by redox titrations three iron-sulfur clusters were identified in their usual redox states, a [3Fe4S] and two [4Fe4S], but also a unique high-potential (HP) state was found. On the basis of (57)Fe Mössbauer spectroscopy we attribute this HP form to a superoxidized state of the [4Fe4S] center proximal to the [NiFe] site. The unique environment of this cluster, characterized by a surplus cysteine coordination, is able to tune the redox potentials and make it compliant with the [4Fe4S](3+) state. It is actually the first example of a biological [4Fe4S] center that physiologically switches between 3+, 2+, and 1+ oxidation states within a very small potential range. We suggest that the (1 + /2+) redox couple serves the classical electron transfer reaction, whereas the superoxidation step is associated with a redox switch against oxidative stress.

  7. A strenuous experimental journey searching for spectroscopic evidence of a bridging nickel–iron–hydride in [NiFe] hydrogenase

    PubMed Central

    Wang, Hongxin; Yoda, Yoshitaka; Ogata, Hideaki; Tanaka, Yoshihito; Lubitz, Wolfgang

    2015-01-01

    Direct spectroscopic evidence for a hydride bridge in the Ni–R form of [NiFe] hydrogenase has been obtained using iron-specific nuclear resonance vibrational spectroscopy (NRVS). The Ni–H–Fe wag mode at 675 cm−1 is the first spectroscopic evidence for a bridging hydride in Ni–R as well as the first iron-hydride-related NRVS feature observed for a biological system. Although density function theory (DFT) calculation assisted the determination of the Ni–R structure, it did not predict the Ni–H–Fe wag mode at ∼675 cm−1 before NRVS. Instead, the observed Ni–H–Fe mode provided a critical reference for the DFT calculations. While the overall science about Ni–R is presented and discussed elsewhere, this article focuses on the long and strenuous experimental journey to search for and experimentally identify the Ni–H–Fe wag mode in a Ni–R sample. As a methodology, the results presented here will go beyond Ni–R and hydrogenase research and will also be of interest to other scientists who use synchrotron radiation for measuring dilute samples or weak spectroscopic features. PMID:26524296

  8. Computational Design of Iron Diphosphine Complexes with Pendant Amines for Hydrogenation of CO2 to Methanol: A Mimic of [NiFe] Hydrogenase.

    PubMed

    Chen, Xiangyang; Jing, Yuanyuan; Yang, Xinzheng

    2016-06-20

    Inspired by the active-site structure of the [NiFe] hydrogenase, we have computationally designed the iron complex [P(tBu) 2 N(tBu) 2 )Fe(CN)2 CO] by using an experimentally ready-made diphosphine ligand with pendant amines for the hydrogenation of CO2 to methanol. Density functional theory calculations indicate that the rate-determining step in the whole catalytic reaction is the direct hydride transfer from the Fe center to the carbon atom in the formic acid with a total free energy barrier of 28.4 kcal mol(-1) in aqueous solution. Such a barrier indicates that the designed iron complex is a promising low-cost catalyst for the formation of methanol from CO2 and H2 under mild conditions. The key role of the diphosphine ligand with pendent amine groups in the reaction is the assistance of the cleavage of H2 by forming a Fe-H(δ-) ⋅⋅⋅H(δ+) -N dihydrogen bond in a fashion of frustrated Lewis pairs. PMID:27225505

  9. Epitaxial Growth of Metastable hcp-Ni and hcp-NiFe Thin Films on Au(100)fcc Single-Crystal Underlayers and Their Structure Characterization

    NASA Astrophysics Data System (ADS)

    Ohtake, Mitsuru; Sato, Yoichi; Higuchi, Jumpei; Tanaka, Takahiro; Kirino, Fumiyoshi; Futamoto, Masaaki

    2011-10-01

    Metastable hcp-Ni and hcp-NiFe epitaxial thin films are prepared on Au(100)fcc single-crystal underlayers by molecular beam epitaxy. The epitaxial growth and the transformation from metastable hcp to more stable fcc phase are studied by in-situ reflection high-energy electron diffraction. In an early stage of film growth, hcp(1120) crystal is stabilized through hetero-epitaxial growth. The epitaxial orientation relationship between the film and the underlayer is determined to be hcp(1120)[0001], hcp(1120)[1100] ∥ Au(100)[001]fcc. With increasing the film thickness, the hcp structure starts to transform into fcc structure. High-resolution transmission electron microscopy shows that the film consists of a mixture of hcp and fcc crystals and that a large number of stacking faults exist parallel to the close-packed plane. The results suggest that the hcp structure starts to transform from these stacking faults into fcc structure in the lateral direction by atomic displacement parallel to the hcp(0001) close-packed plane. The crystallographic orientation relationships between the hcp and transformed fcc crystals are determined to be fcc(110)[111], fcc(110)[111] ∥ hcp(1120)[0001] and fcc(110)[112], fcc(110)[112] ∥ hcp(1120)[1100].

  10. Atomic model of the F420-reducing [NiFe] hydrogenase by electron cryo-microscopy using a direct electron detector.

    PubMed

    Allegretti, Matteo; Mills, Deryck J; McMullan, Greg; Kühlbrandt, Werner; Vonck, Janet

    2014-01-01

    The introduction of direct electron detectors with higher detective quantum efficiency and fast read-out marks the beginning of a new era in electron cryo-microscopy. Using the FEI Falcon II direct electron detector in video mode, we have reconstructed a map at 3.36 Å resolution of the 1.2 MDa F420-reducing hydrogenase (Frh) from methanogenic archaea from only 320,000 asymmetric units. Videos frames were aligned by a combination of image and particle alignment procedures to overcome the effects of beam-induced motion. The reconstructed density map shows all secondary structure as well as clear side chain densities for most residues. The full coordination of all cofactors in the electron transfer chain (a [NiFe] center, four [4Fe4S] clusters and an FAD) is clearly visible along with a well-defined substrate access channel. From the rigidity of the complex we conclude that catalysis is diffusion-limited and does not depend on protein flexibility or conformational changes. DOI: http://dx.doi.org/10.7554/eLife.01963.001. PMID:24569482

  11. Synthesis and characterization of NiFe2O4 electrocatalyst for the hydrogen evolution reaction in alkaline water electrolysis using different polymer binders

    NASA Astrophysics Data System (ADS)

    Chanda, Debabrata; Hnát, Jaromír; Paidar, Martin; Schauer, Jan; Bouzek, Karel

    2015-07-01

    NiFe2O4 electrocatalyst for the hydrogen evolution reaction (HER) has been synthesized using the co-precipitation method of the respective metal ions from water solution. After calcination of the precipitate, the resulting electrocatalyst was characterized by a broad range of techniques to obtain information on its crystallographic structure, specific surface area, morphology and chemical composition. The electrocatalytic activity towards HER in alkaline water electrolysis was investigated by means of linear sweep voltammetry. The catalyst showed promising electrocatalytic properties. Subsequently three types of binders were used to prepare a cathode catalytic layer based on a catalyst synthesized on top of a nickel foam support, namely an anion-selective quaternized poly(phenylene oxide) (qPPO) ionomer, an electroneutral polymer polytetrafluoroethylene and cation-selective Nafion®. The resulting membrane-electrode assemblies (MEAs), based on an anion-selective membrane, were tested in an alkaline water electrolyzer. In a single-cell test the MEA with a qPPO ionomer exhibited higher HER activity compared to the remaining binders tested. The current density obtained using a MEA containing qPPO binder attained a value of 125 mA cm-2 at a cell voltage of 1.85 V. The stability of the MEA containing qPPO binder was examined by continuous operation for 143 h, followed by 55 h intermittent electrolysis.

  12. Discovery of Fe-Ce Oxide/BiVO4 Photoanodes through Combinatorial Exploration of Ni-Fe-Co-Ce Oxide Coatings.

    PubMed

    Shinde, Aniketa; Guevarra, Dan; Liu, Guiji; Sharp, Ian D; Toma, Francesca M; Gregoire, John M; Haber, Joel A

    2016-09-14

    An efficient photoanode is a prerequisite for a viable solar fuels technology. The challenges to realizing an efficient photoanode include the integration of a semiconductor light absorber and a metal oxide electrocatalyst to optimize corrosion protection, light trapping, hole transport, and photocarrier recombination sites. To efficiently explore metal oxide coatings, we employ a high-throughput methodology wherein a uniform BiVO4 film is coated with 858 unique metal oxide coatings covering a range of metal oxide loadings and the full (Ni-Fe-Co-Ce)Ox pseudoquaternary composition space. Photoelectrochemical characterization of the photoanodes reveals that specific combinations of metal oxide composition and loading provide up to a 13-fold increase in the maximum photoelectrochemical power generation for oxygen evolution in pH 13 electrolyte. Through mining of the high-throughput data we identify composition regions that form improved interfaces with BiVO4. Of particular note, integrated photoanodes with catalyst compositions in the range Fe(0.4-0.6)Ce(0.6-0.4)Ox exhibit high interface quality and excellent photoelectrochemical power conversion. Scaled-up inkjet-printed electrodes and photoanodic electrodeposition of this composition on BiVO4 confirms the discovery and the synthesis-independent interface improvement of (Fe-Ce)Ox coatings on BiVO4. PMID:27549019

  13. Micro-focused Brillouin light scattering study of the magnetization dynamics driven by Spin Hall effect in a transversely magnetized NiFe nanowire

    SciTech Connect

    Madami, M. Carlotti, G.; Gubbiotti, G.; Tacchi, S.; Siracusano, G.; Finocchio, G.; Carpentieri, M.

    2015-05-07

    We employed micro-focused Brillouin light scattering to study the amplification of the thermal spin wave eigenmodes by means of a pure spin current, generated by the spin-Hall effect, in a transversely magnetized Pt(4 nm)/NiFe(4 nm)/SiO{sub 2}(5 nm) layered nanowire with lateral dimensions 500 × 2750 nm{sup 2}. The frequency and the cross section of both the center (fundamental) and the edge spin wave modes have been measured as a function of the intensity of the injected dc electric current. The frequency of both modes exhibits a clear redshift while their cross section is greatly enhanced on increasing the intensity of the injected dc. A threshold-like behavior is observed for a value of the injected dc of 2.8 mA. Interestingly, an additional mode, localized in the central part of the nanowire, appears at higher frequency on increasing the intensity of the injected dc above the threshold value. Micromagnetic simulations were used to quantitatively reproduce the experimental results and to investigate the complex non-linear dynamics induced by the spin-Hall effect, including the modification of the spatial profile of the spin wave modes and the appearance of the extra mode above the threshold.

  14. Modeling the active site of [NiFe] hydrogenases and the [NiFeu] subsite of the C-cluster of carbon monoxide dehydrogenases: low-spin iron(II) versus high-spin iron(II).

    PubMed

    Weber, Katharina; Erdem, Özlen F; Bill, Eckhard; Weyhermüller, Thomas; Lubitz, Wolfgang

    2014-06-16

    A series of four [S2Ni(μ-S)2FeCp*Cl] compounds with different tetradentate thiolate/thioether ligands bound to the Ni(II) ion is reported (Cp* = C5Me5). The {S2Ni(μ-S)2Fe} core of these compounds resembles structural features of the active site of [NiFe] hydrogenases. Detailed analyses of the electronic structures of these compounds by Mössbauer and electron paramagnetic resonance spectroscopy, magnetic measurements, and density functional theory calculations reveal the oxidation states Ni(II) low spin and Fe(II) high spin for the metal ions. The same electronic configurations have been suggested for the Cred1 state of the C-cluster [NiFeu] subsite in carbon monoxide dehydrogenases (CODH). The Ni-Fe distance of ∼3 Å excludes a metal-metal bond between nickel and iron, which is in agreement with the computational results. Electrochemical experiments show that iron is the redox active site in these complexes, performing a reversible one-electron oxidation. The four complexes are discussed with regard to their similarities and differences both to the [NiFe] hydrogenases and the C-cluster of Ni-containing CODH.

  15. Tensile behavior of nanocrystalline copper

    SciTech Connect

    Sanders, P.G.; Weertman, J.R.; Eastman, J.A. |

    1995-11-01

    High density nanocrystalline copper produced by inert gas condensation was tested in tension. Displacements were measured using foil strain gauges, which greatly improved the accuracy of the strain data. The Young`s modulus of nanocrystalline copper was found to be consistent with that of coarse-grained copper. Total elongations of {approx} 1% were observed in samples with grain sizes less than 50 nm, while a sample with a grain size of 110 nm exhibited more than 10% elongation, perhaps signifying a change to a dislocation-based deformation mechanism in the larger-grained material. In addition, tensile tests were performed as a function of strain rate, with a possible trend of decreased strength and increased elongation as the strain rate was decreased.

  16. Structural and morphological studies of manganese substituted CoFe2O4 and NiFe2O4 nanoparticles

    NASA Astrophysics Data System (ADS)

    Ranjith kumar, E.; Jayaprakash, R.; Patel, Rajesh

    2013-10-01

    Nanocrystalline manganese substituted cobalt and nickel ferrites have been synthesized through the evaporation method by using egg white. These powders were characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). The XRD pattern of manganese substituted spinel ferrites contains some impurity peaks, which are the decomposition of the ferrites to α-Fe2O3 phase at higher annealing temperature. The microstructure and particle size of the annealed sample analyzed by TEM, which gives the particle size well with XRD. The magnetic properties were measured using Vibrating Sample Magnetometer (VSM). The surface/near-surface chemical states of the nanocrystalline manganese substituted cobalt and nickel ferrites are analyzed by XPS within a range of binding energies of 0-1000 eV.

  17. Tribological behavior of nanocrystalline nickel.

    PubMed

    Guidry, D J; Lian, K; Jiang, J C; Meletis, E I

    2009-07-01

    During the last decade, an intensive investigative effort around the globe has been devoted to the understanding of scale effects on materials properties. In spite of their importance, nanoscale effects on tribological properties have attracted little attention. Such effects are of utmost importance to small scale devices such as nano and micro electromechanical systems that contain nanostructured dynamic components that would be difficult to replace or repair. The significant increase in strength arising from the grain size reduction in the nano domain is expected to impact on mechanical processes at asperity contacts that are dominating wear behavior. In the present work, nanocrystalline Ni produced by electroplating was used as a model system to study scale effects on tribological behavior. It was found that compared to bulk (microcrystalline), nanocrystalline Ni can cause a significant reduction in both, the coefficient of friction and wear rate. A consistent relationship was found between grain size, hardness and tribological behavior. It is suggested that the improved tribological behavior of the nanocrystalline Ni is due to the refinement of mechanical processes inhibiting plastic deformation by extensive dislocation motion leading to fracture events. PMID:19916423

  18. Investigation of alloys for advanced steam cycle superheaters and reheaters

    SciTech Connect

    Swindeman, R.W.; Maziasz, P.J.; Judkins, R.R.

    1988-01-01

    Screening tests were performed on three groups of developmental alloys and compared to the alloy design and performance criteria identified as needed for alloys suitable as superheater/reheater tubing in advanced heat recovery systems. The three alloy groups included modifications of type 316 stainless steel, Fe-20Cr-30Ni alloys, and Ni-Cr-Fe aluminides. The screening tests were performed by the Oak Ridge National Laboratory, several university researchers, and industrial researchers and included fabricability, mechanical properties, weldability, and oxidation behavior. If mildly hot or cold worked, the modified type 316 stainless steels possessed excellent strength and ductility for times to 20,000 h, but possessed marginal weldability and oxidation resistance. The 20Cr-30Ni-Fe alloys also exhibited good strength and ductility, but showed marginal weldability tubing, and were marginal with respect to meeting several of the alloy design criteria. One stainless and one modified alloy 800H were produced as 50-mm-diam. tubing for further evaluation. 24 refs., 14 figs.

  19. Features of primary damage by high energy displacement cascades in concentrated Ni-based alloys

    NASA Astrophysics Data System (ADS)

    Béland, Laurent Karim; Lu, Chenyang; Osetskiy, Yuri N.; Samolyuk, German D.; Caro, Alfredo; Wang, Lumin; Stoller, Roger E.

    2016-02-01

    Alloying of Ni with Fe or Co has been shown to reduce primary damage production under ion irradiation. Similar results have been obtained from classical molecular dynamics simulations of 1, 10, 20, and 40 keV collision cascades in Ni, NiFe, and NiCo. In all cases, a mix of imperfect stacking fault tetrahedra, faulted loops with a 1/3⟨111⟩ Burgers vector, and glissile interstitial loops with a 1/2⟨110⟩ Burgers vector were formed, along with small sessile point defect complexes and clusters. Primary damage reduction occurs by three mechanisms. First, Ni-Co, Ni-Fe, Co-Co, and Fe-Fe short-distance repulsive interactions are stiffer than Ni-Ni interactions, which lead to a decrease in damage formation during the transition from the supersonic ballistic regime to the sonic regime. This largely controls final defect production. Second, alloying decreases thermal conductivity, leading to a longer thermal spike lifetime. The associated annealing reduces final damage production. These two mechanisms are especially important at cascades energies less than 40 keV. Third, at the higher energies, the production of large defect clusters by subcascades is inhibited in the alloys. A number of challenges and limitations pertaining to predictive atomistic modeling of alloys under high-energy particle irradiation are discussed.

  20. Features of primary damage by high energy displacement cascades in concentrated Ni-based alloys

    DOE PAGESBeta

    Béland, Laurent Karim; Lu, Chenyang; Osetskiy, Yuri N.; Samolyuk, German D.; Caro, Alfredo; Wang, Lumin; Stoller, Roger E.

    2016-02-25

    Alloying of Ni with Fe or Co reduces primary damage production under ion irradiation. Similar results have been obtained from classical molecular dynamics simulations of 1, 10, 20, and 40 keV collision cascades in Ni, NiFe, and NiCo. In all cases, a mix of imperfect stacking fault tetrahedra, faulted loops with a 1/3 {111} Burgers vector, and glissile interstitial loops with a 1/2 {110} Burgers vector were formed, along with small sessile point defect complexes and clusters. Primary damage reduction occurs by three mechanisms. First, Ni-Co, Ni-Fe, Co-Co, and Fe-Fe short-distance repulsive interactions are stiffer than Ni-Ni interactions, which leadmore » to a decrease in damage formation during the transition from the supersonic ballistic regime to the sonic regime. This largely controls final defect production. Second, alloying decreases thermal conductivity, leading to a longer thermal spike lifetime. The associated annealing reduces final damage production. These two mechanisms are especially important at cascades energies less than 40 keV. Third, at the higher energies, the production of large defect clusters by subcascades is inhibited in the alloys. A number of challenges and limitations pertaining to predictive atomistic modeling of alloys under high-energy particle irradiation are discussed.« less