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Sample records for 57fe moessbauer studies

  1. 57Fe- and 119Sn-Moessbauer Studies of Tin Doped Chromium Iron Oxides of Composition {alpha}-Cr2-xFexO3

    SciTech Connect

    Helgason, Oern; Berry, Frank J.; Ren Xiaolin; Moyo, Thomas

    2005-04-26

    Tin-doped iron chromium oxides of composition {alpha}-Cr2-xFexO3 prepared by the calcination of precipitates adopt the corundum-related structure. 57Fe Moessbauer spectroscopy shows the materials to be composed of small superparamagnetic particles and no evidence for a Morin transition was observed above 80K. The supertransferred hyperfine magnetic field at the tin site is shown by 119Sn Moessbauer spectroscopy to be less than that experienced in tin-doped {alpha}-Fe2O3.

  2. Constraints on the oxidation state of the mantle: An electrochemical and sup 57 Fe Moessbauer study of mantle-derived ilmenites

    SciTech Connect

    Virgo, D.; Luth, R.W. ); Moats, M.A.; Ulmer, G.C. )

    1988-07-01

    Ilmenite samples from four kimberlite localities were studied using electrochemical, Moessbauer spectroscopic, and microprobe analytical techniques in order to infer the oxidation state of their source regions in the mantle. The values of Fe{sup 3+}/{Sigma}Fe calculated from analyses, using three different electron microanalytical instruments assuming ilmenite stoichiometry, are consistently higher than those derived from the Moessbauer data, by as much as 100%. Furthermore, the range in Fe{sup 3+}/{Sigma}Fe calculated using the analyses from different instruments and/or different correction schemes is nearly as large. Thus Fe{sup 3+}/{Sigma}Fe calculated from microprobe analyses should be taken with caution, even if the precision appears high. {sup 57}Fe Moessbauer spectroscopy on the electrochemical experiment run products demonstrates that Fe{sup 3+}/{Sigma}Fe is significantly lower than it is for the natural C-bearing ilmenites. In contrast, the ilmenite that lacked C did not change Fe{sup 3+}/{Sigma}Fe during the electrochemical experiment. Examination of the reduced samples with SEM established that the natural, single-phase ilmenites exsolved during the electrochemical experiment to form ilmenite{sub ss} + spinel{sub ss}. The initial, reduced trends in the electrochemical experiments for the C-bearing ilmenites are attributed to disequilibrium interactions between the decomposing sample and the evolved gas in the electrochemical cell and do not represent the quenched mantle memory nor the intrinsic f{sub O{sub 2}} of the sample prior to reduction. Furthermore, the oxidized f{sub O{sub 2}} trend is interpreted, for the carbon-bearing samples, are representing the f{sub O{sub 2}} of the ilmenite{sub ss} + spinel{sub ss} assemblage and not the intrinsic f{sub o{sub 2}} of the mantle-derived ilemnite{sub ss}.

  3. Phase evolution in {sup 57}Fe/Al multilayers studied through dc magnetization, conversion electron Moessbauer spectroscopy, and transmission electron microscopy

    SciTech Connect

    Jani, Snehal; Lakshmi, N.; Venugopalan, K.; Sebastian, Varkey; Reddy, V. R.; Gupta, Ajay; Lalla, N. P.

    2008-12-15

    Fe/Al multilayer thin films with an overall atomic concentration ratio of Fe:Al=1:2 have been prepared by ion-beam sputtering. Phase formation and microstructural evolution with thermal annealing have been studied by x-ray reflectivity, cross-sectional transmission electron microscopy, dc magnetization, and conversion electron Moessbauer spectroscopy. These studies show that although the starting composition is Al rich, the intermixing of Fe and Al at the interfaces leads to the formation of a magnetic Fe{sub 3}Al-like region at the interface. Thus, the magnetic contribution in the as-deposited multilayer structure (MLS) is not only from pure Fe but also from an Fe{sub 3}Al-like region formed at the interface. On annealing the MLS, a stable nonmagnetic MLS consisting of intermetallic B2Fe{sub 50}Al{sub 50} separated by thin Al layers is formed. Further annealing only induces better ordering of Fe{sub 50}Al{sub 50} and does not destroy the MLS.

  4. {sup 57}Fe Moessbauer and x-ray magnetic circular dichroism study of magnetic compensation of the rare-earth sublattice in Nd{sub 2-x}Ho{sub x}Fe{sub 14}B compounds

    SciTech Connect

    Chaboy, J.; Piquer, C.; Plugaru, N.; Bartolome, F.; Laguna-Marco, M. A.

    2007-10-01

    We present here a study of the magnetic properties of the Nd{sub 2-x}Ho{sub x}Fe{sub 14}B series. The macroscopic properties of these compounds evolve continuously from those of Nd{sub 2}Fe{sub 14}B to those of Ho{sub 2}Fe{sub 14}B as Ho gradually replaces Nd. The system shows a compensation of the rare-earth sublattice magnetization for a critical concentration, x{sub c}=0.55, that is reflected into the anomalous behavior of both macroscopic and microscopic magnetic probes. The combined analysis of magnetization, {sup 57}Fe Moessbauer spectroscopy and Fe K-edge x-ray magnetic circular dichroism (XMCD) measurements suggests that the origin of the anomalous magnetic behavior found at x{sub c}=0.55 is mainly due to the Ho sublattice. Moreover, the analysis of the Fe K-edge XMCD signals reveal the presence of a rare-earth contribution, reflecting the coupling of the rare-earth and Fe magnetic moments, which can lead to the possibility of disentangling the magnetic behavior of both Fe and R atoms using a single absorption edge.

  5. 57Fe Moessbauer Study of Localization and Valence Sate of Iron Ions in Granular Nanocomposites (FeCoZr)x(Al2O3)100-x for Spintronic Applications

    SciTech Connect

    Saad, Anis; Fedotova, Julia; Kalinin, Jurii; Sitnikov, Alexander; Fedotov, Alexander; Rudov, Denis

    2005-04-26

    The influence of composition of the composite films, containing distributed fragmented components of amorphous metallic alloy CoFeZr and amorphous alumina with particles dimensions of 6-10 nm, on the Moessbauer spectra and hyperfine parameters was investigated. Moessbauer spectroscopy of the (Co0.45Fe0.45Zr0.10)X(Al2O3)1-X studied films with 30 at. % < X < 65 at. % has revealed that the structure of Fe ions coexisted in two valence states -- Fe2+ and Fe3+, the pronounced tendency for increasing Fe3+ fraction with the X increment, disappearance of the singlet connected with the Fe -- containing nanoparticles for the samples with X > 55 %, and lack of the ferromagnetic state in the metallic nanoparticles.

  6. Investigations of Iron Minerals Formed by Dissimilatory Alkaliphilic Bacterium with {sup 57}Fe Moessbauer Spectroscopy

    SciTech Connect

    Chistyakova, N. I.; Rusakov, V. S.; Shapkin, A. A.; Zhilina, T. N.; Zavarzina, D. G.; Kohout, J.

    2010-07-13

    Anaerobic alkaliphilic bacterium of Geoalkalibacter ferrihydriticus type (strain Z-0531), isolated from a bottom sediment sample from the weakly mineralized soda Lake Khadyn, have been analyzed. The strain uses the amorphous Fe(III)-hydroxide (AFH) as an electron acceptor and acetate CH{sub 3}COO{sup -} as an electron donor. Moessbauer investigations of solid phase samples obtained during the process of the bacterium growth were carried out at room temperature, 77.8 K, 4.2 K without and with the presence of an external magnetic field (6 T) applied perpendicular to the {gamma}-bebam.

  7. Structure and oscillational motion of /sup 57/Fe atoms in interstitial sites in Al as determined from interference of Moessbauer. gamma. radiation

    SciTech Connect

    Pauling, L.

    1981-12-01

    The first excited site of the /sup 57/Fe atom entrapped in an interstitial site in aluminum, as reported by W. Petry, G. Vogl, and W. Mansel (Phys. Rev. Lett. 45, 1862 (1980)) from a Moessbauer spectroscopic study of a single crystal, is analyzed by consideration of the value of the Hooke's law constant of the Fe-Al bonds obtained from the values for elemental Fe and Al. The eight wavefunctions for the eightfold nearly degenerate excited state are described as 2s1p1d1f hybrids of three-dimensional harmonic oscillator wavefunctions relative to the center of the undistorted Al/sub 6/ octahedron or as localized 1s functions relative to the center of the distorted octahedron. These considerations provide a qualitative understanding of the observations on this system.

  8. Assessment of the optimum degree of Sr{sub 3}Fe{sub 2}MoO{sub 9} electron-doping through oxygen removal: An X-ray powder diffraction and {sup 57}Fe Moessbauer spectroscopy study

    SciTech Connect

    Lopez, Carlos A.; Viola, Maria del C.; Pedregosa, Jose C.; Mercader, Roberto C.

    2010-10-15

    We describe the preparation and structural characterization by X-ray powder diffraction (XRPD) and Moessbauer spectroscopy of three electron-doped perovskites Sr{sub 3}Fe{sub 2}MoO{sub 9-{delta}} with Fe/Mo = 2 obtained from Sr{sub 3}Fe{sub 2}MoO{sub 9}. The compounds were synthesized by topotactic reduction with H{sub 2}/N{sub 2} (5/95) at 600, 700 and 800 {sup o}C. Above 800 {sup o}C the Fe/Mo ratio changes from Fe/Mo = 2-1 < Fe/Mo < 2. The structural refinements of the XRPD data for the reduced perovskites were carried out by the Rietveld profile analysis method. The crystal structure of these phases is cubic, space group Fm3-bar m, with cationic disorder at the two different B sites that can be populated in variable proportions by the Fe atoms. The Moessbauer spectra allowed determining the evolution of the different species formed after the treatments at different temperatures and confirm that Fe ions in the samples reduced at 600, 700 and 800 {sup o}C are only in the high-spin Fe{sup 3+} electronic state.

  9. Nuclear Bragg scattering studies in [sup 57]Fe with synchrotron radiation

    SciTech Connect

    Haustein, P.E.

    1993-01-01

    Studies of nuclear Bragg x-ray scattering of synchrotron radiation, using crystals of [alpha]-[sup 57]Fe[sub 2]O[sub 3], have been carried out at the NSLS at Brookhaven National Laboratory and at the Cornell University CHESS facility. These studies have demonstrated that nuclear resonance states can be used to produce filtered x-ray beams which have extremely narrow bandwidth, small angular divergence and unique polarization and temporal properties. this combination of characteristics, unobtainable with radioactive sources, makes synchrotron-based Moessbauer spectroscopy feasible and is an important complement to existing methods. A review of the experimental methodology is presented. As well as come suggestions for fuller exploitation of this new technique.

  10. Nuclear Bragg scattering studies in {sup 57}Fe with synchrotron radiation

    SciTech Connect

    Haustein, P.E.

    1993-03-01

    Studies of nuclear Bragg x-ray scattering of synchrotron radiation, using crystals of {alpha}-{sup 57}Fe{sub 2}O{sub 3}, have been carried out at the NSLS at Brookhaven National Laboratory and at the Cornell University CHESS facility. These studies have demonstrated that nuclear resonance states can be used to produce filtered x-ray beams which have extremely narrow bandwidth, small angular divergence and unique polarization and temporal properties. this combination of characteristics, unobtainable with radioactive sources, makes synchrotron-based Moessbauer spectroscopy feasible and is an important complement to existing methods. A review of the experimental methodology is presented. As well as come suggestions for fuller exploitation of this new technique.

  11. Synthesis, structure of [H{sub 3} dien].(MF{sub 6}).H{sub 2}O (M=Cr, Fe) and {sup 57}Fe Moessbauer study of [H{sub 3} dien].(FeF{sub 6}).H{sub 2}O

    SciTech Connect

    Ben Ali, Amor Trang Dang, Minh; Greneche, Jean-Marc; Hemon-Ribaud, Annie; Leblanc, Marc; Maisonneuve, Vincent

    2007-06-15

    Single crystals of [H{sub 3} dien].(FeF{sub 6}).H{sub 2}O (I) and [H{sub 3} dien].(CrF{sub 6}).H{sub 2}O (II) are obtained by solvothermal synthesis under microwave heating. I is orthorhombic (Pna2{sub 1}) with a=11.530(2) A, b=6.6446(8) A, c=13.787(3) A, V=1056.3(2) A{sup 3} and Z=4. II is monoclinic (P2{sub 1} /c) with a=13.706(1) A, b=6.7606(6) A, c=11.3181(9) A, {beta}=99.38(1){sup o}, V=1034.7(1) A{sup 3} and Z=4. The structure determinations, performed from single crystal X-ray diffraction data, lead to the R {sub 1}/wR {sub 2} reliability factors 0.028/0.066 for I and 0.035/0.102 for II. The structures of I and II are built up from isolated FeF{sub 6} or CrF{sub 6} octahedra, water molecules and triprotonated amines. In both structures, each octahedron is connected by hydrogen bonds to six organic cations and two water molecules. The iron-based compound is also characterized by {sup 57}Fe Moessbauer spectrometry: the hyperfine structure confirms the presence of Fe{sup 3+} in octahedral coordination and reveals the existence of paramagnetic spin fluctuations. - Graphical abstract: Moessbauer spectra of [H{sub 3} dien].(FeF{sub 6}).H{sub 2}O.

  12. 57Fe Mössbauer study of the chainpur meteorite

    NASA Astrophysics Data System (ADS)

    Elewa, Nancy N.; Cobas, R.; Cadogan, J. M.

    2016-12-01

    The Chainpur meteorite is one of 23 ordinary chondrites classified as LL3-type (low-Fe & low-metal). It was observed as a shower of stones falling on May 9, 1907 in Uttar Pradesh, India. We report here the characterization of the Fe-bearing phases in this chondrite using 57Fe Mössbauer spectroscopy carried out at 298 K, 120 K, 50 K and 13 K. The paramagnetic doublets of olivine and pyroxene dominate the room temperature spectrum, accounting for around 70 % of the spectral area. Moreover, a doublet present with a spectral area of 5 % and assigned to a superparamagnetic Fe 3+ phase is a consequence of terrestrial weathering. On the basis of the measured 57Fe electric quadrupole splitting of the olivine component at room temperature we estimate the mean Fe:Mg ratio in this meteoritic olivine to be around 35:65 % although there is clearly a wide range of composition. The effects of magnetic ordering of the major components olivine and pyroxene are observed at 13 K.

  13. 237Np and 57Fe Mössbauer study of NpFeGa5

    NASA Astrophysics Data System (ADS)

    Homma, Y.; Nakada, M.; Nakamura, A.; Nasu, S.; Aoki, D.; Sakai, H.; Ikeda, S.; Yamamoto, E.; Haga, Y.; Ōnuki, Y.; Shiokawa, Y.

    2006-02-01

    57Fe and 237Np Mössbauer Ōmeasurements have been performed for NpFeGa5, which is one of the so-called neptunium 1-1-5 compounds. The 57Fe Mössbauer spectra below T N = 118 K show the magnetically ordered state. The magnitude of the hyperfine magnetic field at the 57Fe nucleus is determined to be 1.98 ± 0.05 T at 10 K. From the 237Np Mössbauer spectrum at 10 K, the hyperfine magnetic field at the 237Np nucleus is 203 T and the hyperfine coupling constant is determined to be 237 T/μB using the Np atomic magnetic moment of 0.86 μB determined by the neutron diffraction study.

  14. 237Np and 57Fe Mdssbauer study of NpFeGa5

    NASA Astrophysics Data System (ADS)

    Homma, Y.; Nakada, M.; Nakamura, A.; Nasu, S.; Aoki, D.; Sakai, H.; Ikeda, S.; Yamamoto, E.; Haga, Y.; Onuki, Y.; Shiokawa, Y.

    57Fe and 237Np Mössbauer Omeasurements have been performed for NpFeGa5, which is one of the so-called neptunium 1-1-5 compounds. The 57Fe Mössbauer spectra below T N=118 K show the magnetically ordered state. The magnitude of the hyperfine magnetic field at the 57Fe nucleus is determined to be 1.98 ± 0.05 T at 10K. From the 237Np Mössbauer spectrum at 10 K, the hyperfine magnetic field at the 237Np nucleus is 203 T and the hyperfine coupling constant is determined to be 237 T/μB using the Np atomic magnetic moment of 0.86 μB determined by the neutron diffraction study.

  15. {sup 57}Fe NMR study of multiferroic BiFeO{sub 3}

    SciTech Connect

    Pokatilov, V. S. Sigov, A. S.

    2010-03-15

    The effects of the {sup 57}Fe isotope content and high-frequency magnetic field amplitude h{sub 1} on the shape of the NMR spectrum of multiferroic BiFeO{sub 3} at T = 4.2 K are studied by pulsed nuclear magnetic resonance. The NMR spectrum shape and transverse relaxation time T{sub 2} are found to depend strongly on the {sup 57}Fe isotope content and h{sub 1} in multiferroic BiFeO{sub 3} in the presence of a spatial spin-modulated structure of a cycloid type. In a sample with a high {sup 57}Fe isotope content, the Suhl-Nakamura interaction contributes substantially to T{sub 2}. When these dynamic effects are taken into account for analysis of the NMR spectrum shape, an undisturbed (without an anharmonicity effect) spatial spin-modulated structure of a cycloid type is shown to exist in BiFeO{sub 3}.

  16. 57Fe quadrupole splitting and isomer shift in various oxyhemoglobins: study using Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Oshtrakh, M. I.; Berkovsky, A. L.; Kumar, A.; Kundu, S.; Vinogradov, A. V.; Konstantinova, T. S.; Semionkin, V. A.

    2010-04-01

    A comparative study of normal human, rabbit and pig oxyhemoglobins and oxyhemoglobin from patients with chronic myeloleukemia and multiple myeloma using Mössbauer spectroscopy with a high velocity resolution demonstrated small variations of the 57Fe quadrupole splitting and isomer shift. These variations may be a result of small structural differences in the heme iron stereochemistry of various hemoglobins.

  17. 57Fe Mössbauer study of Lu2Fe3Si5 iron silicide superconductor

    DOE PAGES

    Ma, Xiaoming; Ran, Sheng; Pang, Hua; ...

    2015-03-28

    With the advent of Fe–As based superconductivity it has become important to study how superconductivity manifests itself in details of 57Fe Mössbauer spectroscopy of conventional, Fe-bearing superconductors. The iron-based superconductor Lu2Fe3Si5 has been studied by 57Fe Mössbauer spectroscopy over the temperature range from 4.4 K to room temperature with particular attention to the region close to the superconducting transition temperature (Tc=6.1 K). Consistent with the two crystallographic sites for Fe in this structure, the observed spectra appear to have a pattern consisting of two doublets over the whole temperature range. Furthermore, the value of Debye temperature was estimated from temperaturemore » dependence of the isomer shift and the total spectral area and compared with the specific heat capacity data. Neither abnormal behavior of the hyperfine parameters at or near Tc, nor phonon softening were observed.« less

  18. Quadrupolar interaction of ^57Fe in compounds RENi_2B_2C: Experimental and Theoretical Studies

    NASA Astrophysics Data System (ADS)

    Zeng, Zhi; Guenzburger, Diana; Sanchez, D. R. S.; Bud'Ko, S. L.; Fontes, Magda B.; Baggia-Saitovitch, E. M.; Ellis, D. E.

    1996-03-01

    ^57Fe Mössbauer spectra were taken with the RE(Ni_0.99^57Fe_0.01)_2B_2C (RE=Tb, Dy, Ho, Er) samples in a variable temperature helium crysostat to study the interplay between superconductivity and magnetism in the RENi_2B_2C (RE=Dy, Ho, Er, Tm) compounds. The rare earth dependent quadrupole splitting (QS) from ^57Fe Mössbauer spectra decreases with the lanthanide contraction^footnotetext^The lanthanide contraction causes an increase in the ratio c/a along the RE series. from QS=0.27mm/s for TbNi_2B_2C to QS=0.14mm/s for ErNi_2B_2C. Self-consistent frist-principles electronic structure calculation[1] were performed for clusters with 71 atoms (Fe-12RE-14Ni-32B-12C), which were embedded in the charge denisity of several shells of neighbours in the crystal, representing the doped compounds RE(Ni_0.93Fe_0.07)_2B_2C (RE=Gd, Tb, Dy, Ho, and Er). The quadrupole splitting was obtained with the nuclear quadrupole moment Q=0.16b of ^57Fe[2]. The calculated results are in good agreement with experiment. The theoretical results give negative signs for all the QS values; which have not been determined by experiment, except for the compounds with Tb and Ho, for which they are negative. REFERENCES D.E. Ellis, Int. J. Quant. Chem. Suppl. 2, 35(1968); D.E. Ellis and G.S. Painter, Phys. Rev. B, 2, 2887(1970). Ohilipp Dufek, Peter Blaha and K. Schwarz, Phys. Rev. Lett. 75, 3545(1995).

  19. Mössbauer study 57Fe in ultrathin trilayer films with sharp and rough interfaces

    NASA Astrophysics Data System (ADS)

    Pogorily, A. N.; Bondarkova, G. V.; Razumov, O. N.; Shypil, E. V.

    2011-04-01

    Trilayer thin films Py/57Fe/Gd and Gd/57Fe/Py (Py: Fe20Ni80 permalloy) have been prepared by electron-beam evaporation and investigated using conversion-electron Mössbauer spectroscopy (CEMS), scanning tunneling microscopy (STM), polar magneto-optical Kerr effect (PMOKE), and ferromagnetic resonance (FMR). It was shown that the films deposited in the same vacuum and temperature runs but with the reverse order of the layers gave a different quality of interfaces: sharp (Py/57Fe/Gd) and rough (Gd/57Fe/Py). Different distribution of atoms in sharp and rough interfaces results in different magnetic properties: the Mössbauer spectra, FMR, and PMOKE data show the appearance of perpendicular magnetic anisotropy (PMA) and enhancement of magnetization in the samples with the rough Gd/Py interface.

  20. Magnetic behaviour and DCEMS study of SnO2 films implanted with 57Fe

    NASA Astrophysics Data System (ADS)

    Nomura, K.; Iio, S.; Hirose, Y.; Reuther, H.; Nakanishi, A.

    2013-04-01

    Fe implanted SnO2 films (5 × 1016 and 1 × 1017 57Fe ions/cm2) characterized by conversion electron Mossbauer spectroscopy (CEMS) are reviewed. The substrate temperatures affect the growth of precipitated iron oxides. The Fe ion implanted film at room temperature (RT) shows no Kerr effect and no magnetic sextet in CEM spectra. The SnO2 film implanted with 57Fe at the substrate temperature of 300 °C show a small Kerr effect although the magnetic sextet is not observed, but post-annealing results in the disappearance of the Kerr effect. This magnetism is considered to be due to defect induced magnetism. Some samples were measured by CEMS at 15 K. SnO2 (0.1 at %Sb and 3 at %Sb) films, implanted at 500 °C and the post-annealed samples, show RT ferromagnetism due to formation of clusters of magnetite and maghemite, respectively. The layer by layer analysis of these films within 100 nm in thickness has been done by depth sensitive CEMS (DCEMS) using a He + 5 % CH4 gas counter. The structures and compositions of Fe implanted SnO2 films, and the effects due to post-annealing were investigated.

  1. An 57Fe Mössbauer study of three Australian L5 ordinary-chondrite meteorites: dating Kinclaven-001

    NASA Astrophysics Data System (ADS)

    Cadogan, J. M.; Rebbouh, L.; Mills, J. V. J.; Bland, P. A.

    2013-12-01

    Three L5-type ordinary chondrite meteorites recovered from the Nullarbor Region of Western Australia were studied by 57Fe Mössbauer spectroscopy: Kinclaven-001, Camel Donga-007 and Gunnadorah-002. The relative amounts of the various Fe-bearing phases including the primary minerals (Olivine, Pyroxene, Troilite and Fe-Ni metal) and the ferric alteration products (Goethite, Maghemite/Magnetite) were obtained to determine the percentage of iron converted to Fe3 + by weathering processes. These data allow us to estimate the terrestrial age of Kinclaven-001 at 1,700 ± 1,300 yrs.

  2. Magnetic anisotropy in FeSb studied by 57Fe Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Komędera, K.; Jasek, A. K.; Błachowski, A.; Ruebenbauer, K.; Krztoń-Maziopa, A.

    2016-02-01

    The Fe1+xSb compound has been synthesized close to stoichiometry with x=0.023(8). The compound was investigated by 57Fe Mössbauer spectroscopy in the temperature range 4.2-300 K. The antiferromagnetic ordering temperature was found as 232 K i.e. much higher than for the less stoichiometric material. Regular iron was found to occupy two different positions in proportion 2:1. They differ by the electric quadrupole coupling constants and both of them exhibit extremely anisotropic electric field gradient tensor (EFG) with the asymmetry parameter η ≈ 1 . The negative component of both EFGs is aligned with the c-axis of the hexagonal unit cell, while the positive component is aligned with the <120> direction. Hence, a model describing deviation from the NiAs P63/mmc symmetry group within Fe-planes has been proposed. Spectra in the magnetically ordered state could be explained by introduction of the incommensurate spin spirals propagating through the iron atoms in the direction of the c-axis with a complex pattern of the hyperfine magnetic fields distributed within a-b plane. Hyperfine magnetic field pattern of spirals due to major regular iron is smoothed by the spin polarized itinerant electrons, while the minor regular iron exhibits hyperfine field pattern characteristic of the highly covalent bonds to the adjacent antimony atoms. The excess interstitial iron orders magnetically at the same temperature as the regular iron, and magnetic moments of these atoms are likely to form two-dimensional spin glass with moments lying in the a-b plane. The upturn of the hyperfine field for minor regular iron and interstitial iron is observed below 80 K. Magneto-elastic effects are smaller than for FeAs, however the recoilless fraction increases significantly upon transition to the magnetically ordered state.

  3. Single-crystalline M-type Sr Hexaferrites studied by 57Fe Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Nagasawa, Nobumoto; Ikeda, Shugo; Shimoda, Aiko; Waki, Takeshi; Tabata, Yoshikazu; Nakamura, Hiroyuki; Kobayashi, Hisao

    2016-12-01

    The 57Fe Mössbauer spectra of the single crystalline and the finely ground Sr1- x La x Fe12- y Co y O19 ( x = 0 : y = 0, x = 0.192 : y = 0.152 and x = 0.456 : y = 0.225) samples have been measured to investigate the La-Co substitution effects. All observed spectra at 150 K were well fitted using the five subspectra which correspond to the five crystallographical nonequivalent Fe sites in the M-type hexaferrite, indicating that the valence changes to Fe2+ ions in the Fe3+ ions were not observed in our Sr1- x La x Fe12- y Co y O19 samples. In SrFe12O19, the relative absorption intensities in the five subspectra show the large anisotropies in the recoilless fractions at the five Fe sites whereas these anisotropies were not observed in Sr0.544La0.456Fe11.775Co0.225O19. These results indicate the chemical compositional dependence on the anisotropies of the recoilless fractions at the five Fe sites. The substitution of a Co2+ ion for the Fe3+ ion changes the center shifts of the Fe3+ ions near the Co2+ ion by the perturbation of the Fe-O-Co hybridizations. Therefore, the Co2+ ions occupy the 4 f 1 and the 4 f 2 sites due to the chemical compositional dependences of the refined magnetic hyperfine field and center shifts of the Fe3+ ions.

  4. 57Fe-NMR study on iron-oxypnictide superconductor LaFeAsO1-y

    NASA Astrophysics Data System (ADS)

    Mukuda, H.; Terasaki, N.; Yashima, M.; Kitaoka, Y.; Miyazawa, K.; Shirage, P. M.; Suzuki, S.; Miyasaka, S.; Tajima, S.; Kito, H.; Eisaki, H.; Iyo, A.

    2010-01-01

    We report systematic 57Fe-NMR study on an underdoped sample (Tc = 20 K), an optimally doped sample (Tc = 28 K), and an overdoped sample (Tc = 22 K) of oxygen-deficient iron (Fe)-based oxypnictide superconductor LaFeAsO1-y. The 57Fe-1/T1T in the normal state decreases significantly upon cooling regardless of an electron-doping level, revealing that 1/T1T is not always enhanced by antiferromagnetic fluctuations close to an antiferromagnetic phase in the underdoped superconducting sample. This contrasts with the behavior in hole-doped Ba0.6K0.4Fe2As2(Tc = 38 K), which exhibits a significant increase in 1/T1T upon cooling. We suggest that the crucial difference between the normal-state properties of LaFeAsO1-yand Ba0.6K0.4Fe2As2 originates from the fact that the relevant Fermi surface topologies are differently modified depending on whether electrons or holes are doped into the FeAs layers.

  5. Moessbauer effect: Study of disordered magnetic systems

    SciTech Connect

    Chang, Xiao Sha.

    1989-01-01

    This dissertation describes Moessbauer spectroscopy studies of two chemically disordered binary, crystalline alloys having the composition A{sub 1-x}B{sub x}. Both systems are random 3d Heisenberg ferromagnets. In each case both A and B atoms carry a magnetic moment. The first study concerns a Moessbauer absorber experiment on Fe{sub 1-x} V{sub x}, in which the disorder in the critical region is of the annealed random exchange type. To eliminate the effect of concentration inhomogeneity, the measurement of the critical exponent {beta} was done on the alloy with x = 0.125, where dT{sub C}/dx = 0, yielding {beta} = 0.362(8) over the reduced temperature range 1.4 {times} 10{sup {minus}3} < t < 4.88 {times} 10{sup {minus}1}. This result confirms the theoretical prediction that the annealed disorder is irrelevant to critical behavior in this case. As expected the critical exponent {beta} is consistent with the expectation for the 3d Heisenberg model as well as the measured exponent of pure Fe. The second study involves a Moessbauer source experiment on {sup 57} CoPd{sub 0.80}Co{sub 0.20}, in which disorder is of the quenched random exchange type perturbed by a very weak random anisotropy interaction. The critical exponent {beta} deduced over the range 1 {times} 10{sup {minus}2} < t < 2 {times} 10{sup {minus}1} is 0.385(20), and is consistent with the theoretical prediction for quenched disordered 3d Heisenberg systems: the disorder is irrelevant to the critical behavior. However, because of the restricted range of reduced temperature, the result is insufficiently asymptotic to serve as a conclusive test of the theory. Outside the critical region the distribution of Fe{sup 57} hyperfine field in Pd{sub 0.80}Co{sub 0.20} is observed to have an anomalous temperature dependence characterized by a linear increase in the width of the field distribution for T/T{sub C} {ge} 0.6.

  6. Low temperature Raman and high field 57Fe Mossbauer study of polycrystalline GaFeO3.

    PubMed

    Sharma, Kavita; Raghavendra Reddy, V; Kothari, Deepti; Gupta, Ajay; Banerjee, A; Sathe, V G

    2010-04-14

    The magnetic and phonon properties of polycrystalline magnetoelectric/multiferroic GaFeO(3) are studied. Using high field (57)Fe Mossbauer spectroscopy, occupation of Fe is observed at four cation sites. A Fe population of about 6% is observed at the tetrahedral Ga1 site, which explains the observed pinched-like M-H curve and initial sharp increase of the magnetization. The calculated net magnetization value from Mossbauer data suggests that the Fe moment at the Ga1 site is parallel to Fe1 and opposite to that of Fe2 and Ga2 sites, resulting in ferrimagnetism. From low temperature Raman data, anomalous temperature variation in frequency at T(C) is observed for the mode at ∼700 cm(-1).

  7. Mechanically-induced disorder in CaFe2As2: A 57Fe Mössbauer study

    DOE PAGES

    Ma, Xiaoming; Ran, Sheng; Canfield, Paul C.; ...

    2015-10-17

    57Fe Mössbauer spectroscopy was used to perform a microscopic study on the extremely pressure and strain sensitive compound, CaFe2As2, with different degrees of strain introduced by grinding and annealing. At the base temperature, in the antiferromagnetic/orthorhombic phase, compared to a sharp sextet Mössbauer spectrum of single crystal CaFe2As2, which is taken as an un-strained sample, an obviously broadened sextet and an extra doublet were observed for ground CaFe2As2 powders with different degrees of strain. The Mössbauer results suggest that the magnetic phase transition of CaFe2As2 can be inhomogeneously suppressed by the grinding induced strain to such an extent that themore » antiferromagnetic order in parts of the grains forming the powdered sample remain absent all the way down to 4.6 K. However, strain has almost no effect on the temperature dependent hyperfine magnetic field in the grains with magnetic order. Additional electronic and asymmetry information was obtained from the isomer shift and quadrupole splitting. Similar isomer shift values in the magnetic phase for samples with different degrees of strain, indicate that the stain does not bring any significant variation of the electronic density at 57Fe nucleus position. As a result, the absolute values of quadrupole shift in the magnetic phase decrease and approach zero with increasing degrees of strain, indicating that the strain reduces the average lattice asymmetry at Fe atom position.« less

  8. Hyperfine Interactions of 57Fe Nuclei in the Study of Interdiffusion Phenomena and Phase Formation

    NASA Astrophysics Data System (ADS)

    Carbucicchio, M.; Palombarini, G.; Rateo, M.

    1998-07-01

    The effects of interdiffusion phenomena and reactions occurring in the early stages of the interaction at 1273 K between iron and chromium monoborides were studied by transmission Mössbauer and X-ray diffraction techniques, and modifications occurring in Fe/Al multilayers during both deposition and subsequent thermal aging at 400 K in vacuum or air were studied by conversion electron Mössbauer and Auger electron depth profiling techniques. In both cases the main objective of the work was to obtain a better understanding of the mechanisms of modification of the materials under examination with a view towards improving the properties of materials and coatings for specific applications.

  9. Superconducting state of iron arsenide Ba1-xFeAs: 57Fe and 75As NMR studies

    NASA Astrophysics Data System (ADS)

    Nishimura, H.; Yashima, M.; Mukuda, H.; Kitaoka, Y.; Miyazawa, K.; Shirage, P. M.; Kiho, K.; Kito, H.; Eisaki, H.; Iyo, A.

    2010-12-01

    We report 57Fe and 75As NMR measurements of the novel normal and superconducting-state characteristics of the iron-arsenide superconductor BaKFeAsTc=38K. In the normal state, the measured Knight shift and nuclear spin-lattice relaxation rate (1/T1) demonstrate the development of wave-number (q)-dependent spin fluctuations, except at q=0, which may originate from the nesting across the disconnected Fermi surfaces. In the superconducting state, the spin component in the 57Fe-Knight shift decreases down to zero with decreasing T, evidencing that a spin-singlet superconducting state is realized in BaKFeAs.

  10. 57Fe Mössbauer Studies in Mo Fe Supported Catalysts

    NASA Astrophysics Data System (ADS)

    Castelão-Dias, M.; Costa, B. F. O.; Quinta-Ferreira, R. M.

    2001-09-01

    Industrially, the Mo Fe catalysts used in the selective oxidation of methanol to formaldehyde can rapidly deactivate. The use of support materials may reduce the high temperatures in the catalytic bed and/or increase thermal and mechanical resistance. However, during the preparation of these catalysts, or even during reaction conditions, the active species may react with the support material losing their catalytic activity. In this work silica, silicium carbide and titania were studied as supported catalysts by Mössbauer spectroscopy which proved to be a useful technique in the choice of supported materials.

  11. Selected applications of 57Fe Mössbauer spectroscopy to mineral studies

    NASA Astrophysics Data System (ADS)

    de Grave, E.; Eeckhout, S. G.; McCammon, C. A.

    1999-11-01

    The microscopic models which are commonly used to interpret the temperature variations of the centre shifts and quadrupole splittings observed from the Mössbauer spectra of iron-containing minerals are briefly presented and illustrated using the results of recent studies of ortho- and clinopyroxenes. The importance of applied-field Mössbauer spectroscopy for the determination of the electric field gradient is indicated. Aspects of the magnetic spectra of Fe2+-bearing minerals emphasise the benefit of using external fields to elucidate the nature of the magnetic ordering. Two Fe3+ minerals, bernalite and franklinite, serve as examples to illustrate this point. Finally, two applications of the Mössbauer milliprobe technique are presented: the characterisation of inclusions in diamond, and the determination of the oxidation state of a new iron uranyl sulfate mineral, deliensite.

  12. Iron nano-clusters in ytterbium films: a 57Fe Mössbauer spectroscopic study

    NASA Astrophysics Data System (ADS)

    Rojas-Ayala, C.; Herrera, W. T.; Dinóla, I. S.; Kraken, M.; Passamani, E. C.; Baggio-Saitovitch, E.; Litterst, F. J.

    2014-01-01

    We have performed a Mössbauer study on iron clusters that are formed in ytterbium films prepared by vapor co-deposition onto kapton substrates kept at room temperature. The film thicknesses were chosen in a range between 2.5 and 2.8 m. XRD of the films reveals a mixture of fcc- and hcp-like ytterbium. Iron concentrations were between 0.3 and 5 at %. All samples reveal hyperfine spectra attributed to only two types of iron clusters with well defined hyperfine parameters. The clusters are supposed to be formed at boundaries of hcp- and fcc-like grains. In addition there is found a small contribution from monomeric iron. Spectra taken at 4.2 K reveal a complex distribution of magnetic hyperfine fields. The dynamic origin of the spectral shape is supported by susceptibility data revealing spin-freezing at temperatures below ca. 10 K. This proves that the iron clusters have sizes on the order of nm.

  13. Mechanically - induced disorder in CaFe2As2: a 57Fe Mössbauer study

    NASA Astrophysics Data System (ADS)

    Ma, Xiaoming; Ran, Sheng; Canfield, Paul C.; Bud'Ko, Sergey L.

    57 Fe Mössbauer spectroscopy was used to study an extremely pressure and strain sensitive compound, CaFe2As2, with different degrees of strain introduced by grinding and annealing. At the base temperature, in the antiferromagnetic/orthorhombic phase, compared to a sharp sextet Mössbauer spectrum of single crystal CaFe2As2, which is taken as an un-strained sample, an obviously broadened sextet and an extra doublet were observed for ground CaFe2As2 powders with different degrees of strain. The Mössbauer results suggest that the magnetic phase transition of CaFe2As2 can be inhomogeneously suppressed by the grinding induced strain to such an extent that the antiferromagnetic order in parts of the grains forming the powdered sample remain absent all the way down to 4.6 K. However, strain has almost no effect on the temperature dependent hyperfine magnetic field in the grains with magnetic order. The quadrupole shift in the magnetic phase approachs zero with increasing degrees of strain, indicating that the strain reduces the average lattice asymmetry at Fe atom position. Supported by US DOE under the Contract No. DE-AC02-07CH11358 and by the China Scholarship Council.

  14. Single-Crystal 57Fe Q-Band ENDOR Study of the 4 Iron-4 Sulfur Cluster in its Reduced [4Fe-4S] 1+ State

    NASA Astrophysics Data System (ADS)

    Moriaud, Fabrice; Gambarelli, Serge; Lamotte, Bernard; Mouesca, Jean-Marie

    2001-12-01

    57Fe Q-band ENDOR has been used to study the [4Fe-4S]1+ state created by γ irradiation of single crystals of the synthetic model compound [N(C2H5)4]2[Fe4S4(SCH2C6H5)4] enriched in 57Fe. This compound is an excellent biomimetic model of the active sites of many 4 iron-4 sulfur proteins, enabling detailed and systematic studies of its oxidized [4Fe-4S]3+ and reduced [4Fe-4S]1+ paramagnetic states. Taking advantage of the fact that Q-band ENDOR, in contrast with X-Band ENDOR, allows for a very good separation of the 57Fe transitions from those of the protons, the complete hyperfine tensors of the four iron atoms for the [4Fe-4S]1+ species has been measured with precision. For each iron atom, the electron orbital and electron spin isotropic contributions have been determined separately. Moreover, it is remarkable that two 57Fe hyperfine tensors attributed to the ferrous pair of iron atoms are very different. In effect, one tensor presents a much larger anisotropic part and a much smaller isotropic part than those of the other. This difference has been interpreted in terms of a differential electron orbital hyperfine interaction among the two ferrous ions.

  15. Fe-57 Moessbauer study of tektites

    NASA Technical Reports Server (NTRS)

    Evans, B. J.; Leung, L. K.

    1976-01-01

    Moessbauer measurements were made on selected moldavite, australite, philippinite, and Georgia tektites. The spectra consist of two apparent lines, but at least two quadrupole doublets can be fitted to these spectra. The Moessbauer parameters for these doublets indicate that they arise from Fe2+ ions with local environments, which are relatively rich and relatively poor in calcium, respectively, similar to those in clinopyroxenes. No evidence for Fe3+/Fe2+ ratios above 0.01 (estimated detection limit) have been found in any tektite. Tektites are considerably more reduced than previously believed, and the extent of the reduction shows little or no variation among different types of tektites. These results limit the source materials of tektites to minerals in which the iron is uniformly highly reduced and in which the iron is contained clinopyroxene-like phases.

  16. A study of thermodynamic properties of dilute Fe-Ru alloys by 57Fe Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Idczak, R.; Konieczny, R.; Chojcan, J.

    2016-12-01

    The room temperature Mössbauer spectra of 57Fe were measured for Fe1- x Ru x solid solutions with x in the range 0.01 ≤ x ≤ 0.08. The obtained data were analysed in terms of short-range order parameter (SRO) and the binding energy E b between two ruthenium atoms in the studied materials using the extended Hrynkiewicz-Królas idea. The extrapolated value of E b for x = 0 was used to compute the enthalpy of solution H FeRu of Ru in Fe matrix. The result was compared with corresponding values given in the literature which were derived from experimental calorimetric data as well as with the value resulting from the cellular atomic model of alloys by Miedema. It was found that all the H FeRu values are negative or Ru atoms interact repulsively. At the same time, the Mössbauer data were used to determine values of the short-range order parameter α 1. For the as-obtained samples in which atoms are frozen-in high temperature state, close to the melting point, the negative α 1 values were found. The findings indicates ordering tendencies in such specimens. On the other hand, in the case of the annealed samples where the observed distributions of atoms should be frozen-in state corresponding to the temperature 700 K, the Fe1- x Ru x alloys with x ≥ 0.05 exhibit clustering tendencies (a predominance of Fe-Fe and Ru-Ru bonds), which manifest themselves by positive values of the calculated SRO parameter. The clustering process leads to a local increase in ruthenium concentration and nucleation of a new ruthenium-rich phase with the hcp structure.

  17. Study of 57Fe Mössbauer effect in RFe2Zn20 ( R = Lu, Yb, Gd)

    DOE PAGES

    Bud’ko, Sergey L.; Kong, Tai; Ma, Xiaoming; ...

    2015-08-04

    In this document we report measurements of 57Fe Mössbauer spectra for RFe2Zn20 (R = Lu, Yb, Gd) from ~ 4.5 K to room temperature. The obtained isomer shift values are very similar for all three compounds, their temperature dependence was analyzed within the Debye model and resulted in an estimate of the Debye temperatures of 450-500 K. The values of quadrupole splitting at room temperature change with the cubic lattice constant a in a linear fashion. For GdFe2Zn20, ferromagnetic order is seen as an appearance of a sextet in the spectra. The 57Fe site hyperfine field for T → 0more » was evaluated to be ~ 2.4 T.« less

  18. Study of 57 Fe Mössbauer effect in RFe2Zn20 ( R = Lu, Yb, Gd)

    DOE PAGES

    Bud’ko, Sergey L.; Kong, Tai; Ma, Xiaoming; ...

    2015-08-04

    In this document we report measurements of 57Fe Mössbauer spectra for RFe2Zn20 (R = Lu, Yb, Gd) from ~ 4.5 K to room temperature. The obtained isomer shift values are very similar for all three compounds, their temperature dependence was analyzed within the Debye model and resulted in an estimate of the Debye temperatures of 450-500 K. The values of quadrupole splitting at room temperature change with the cubic lattice constant a in a linear fashion. For GdFe2Zn20, ferromagnetic order is seen as an appearance of a sextet in the spectra. The 57Fe site hyperfine field for T → 0more » was evaluated to be ~ 2.4 T.« less

  19. Mössbauer spectroscopic study of 57Fe metabolic transformations in the rhizobacterium Azospirillum brasilense Sp245

    NASA Astrophysics Data System (ADS)

    Kamnev, Alexander A.; Tugarova, Anna V.; Kovács, Krisztina; Biró, Borbála; Homonnay, Zoltán; Kuzmann, Ernő

    2014-04-01

    Preliminary 57Fe transmission Mössbauer spectroscopic data were obtained for the first time for live cells of the plant-growth-promoting rhizobacterium Azospirillum brasilense (wild-type strain Sp245) grown aerobically with 57FeIII-nitrilotriacetate (NTA) complex as a sole source of iron. The results obtained have shown that live cells actively reduce part of the assimilated iron(III) to iron(II), the latter amounting up to 33 % of total cellular iron after 18 h of growth, and 48 % after additional 3 days of storage of the dense wet cell suspension in nutrient-free saline solution in air at room temperature (measured at 80 K). The cellular iron(II) was found to be represented by two quadrupole doublets of different high-spin forms, while the parameters of the cellular iron(III) were close to those typical for bacterioferritins.

  20. Moessbauer Study of Electrodeposited Fe/Fe-Oxide Multilayers

    SciTech Connect

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

    2005-04-26

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

  1. The role of alpha-iron and cementite phases in the growing mechanism of carbon nanotubes: a 57Fe Mössbauer spectroscopy study.

    PubMed

    Pérez-Cabero, M; Taboada, J B; Guerrero-Ruiz, A; Overweg, A R; Rodríguez-Ramos, I

    2006-03-14

    57Fe Mössbauer spectroscopy was used to study the reduction behavior at temperatures as high as 1073 K of an iron/silica catalyst, and also the carbonaceous materials isolated after acetylene decomposition over this catalyst at several temperatures (873-1073 K). The products were previously characterized by transmission electron microscopy and it was clearly proven that the concentration of carbon nanotubes increased when reaction reached highest temperatures. This was related with an increment in cementite concentration (generated from initial alpha-iron and the progressive reduction of the remnant Fe+2 caused by acetylene decomposition) as detected by 57Fe Mössbauer. These results undoubtedly revealed the role of alpha-iron as active center for acetylene decomposition and cementite as main carbide intermediate species in the catalytic growth of CNTs.

  2. 57Fe75Mo8Cu1B16 metallic glass studied by CEMS, CXMS and HEXRD

    NASA Astrophysics Data System (ADS)

    Cesnek, Martin; Miglierini, Marcel; Bednarčík, Jozef

    2016-10-01

    57Fe75Mo8Cu1B16 metallic glass prepared by single roller melt spinning was investigated by conversion electron Mössbauer spectroscopy, conversion X-ray Mössbauer spectroscopy and high-energy X-ray diffraction. All methods confirmed presence of amorphous structure without traces of a crystalline phase. Results obtained by Mössbauer spectrometry suggest predominant appearance of magnetic regions on side of the ribbon which was in contact with the quenching wheel. In situ High-energy X-ray diffraction experiment revealed transition from ferromagnetic to paramagnetic state and it was even possible to estimate the Curie temperature.

  3. Progressive Oxidation of Pyrite in Five Bituminous Coal Samples: An As XANES and 57Fe Mossbauer Spectroscopic Study

    SciTech Connect

    Kolker,A.; Huggins, F.

    2007-01-01

    Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period of 17 months. Samples investigated include a Springfield coal from Indiana (whole coal pyritic S = 2.13 wt.%; As in pyrite = detection limit (d.l.) to 0.06 wt.%), two Pittsburgh coal samples from West Virginia (pyritic S = 1.32-1.58 wt.%; As in pyrite = d.l. to 0.34 wt.%), and two samples from the Warrior Basin, Alabama (pyritic S = 0.26-0.27 wt.%; As in pyrite = d.l. to 2.72 wt.%). Samples were collected from active mine faces, and expected differences in the concentration of As in pyrite were confirmed by electron microprobe analysis. Experimental weathering conditions in test chambers were maintained as follows: (1) dry Ar atmosphere; (2) dry O{sub 2} atmosphere; (3) room atmosphere (relative humidity {approx}20-60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and {sup 57}Fe Mossbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. {sup 57}Fe Mossbauer spectroscopy also shows a much greater proportion of Fe{sup 3+} forms (jarosite, Fe{sup 3+} sulfate, FeOOH) for samples stored under wet conditions, but much less

  4. Progressive oxidation of pyrite in five bituminous coal samples: An As XANES and 57Fe Mössbauer spectroscopic study

    USGS Publications Warehouse

    Kolker, Allan; Huggins, Frank E.

    2007-01-01

    Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period of 17 months. Samples investigated include a Springfield coal from Indiana (whole coal pyritic S = 2.13 wt.%; As in pyrite = detection limit (d.l.) to 0.06 wt.%), two Pittsburgh coal samples from West Virginia (pyritic S = 1.32–1.58 wt.%; As in pyrite = d.l. to 0.34 wt.%), and two samples from the Warrior Basin, Alabama (pyritic S = 0.26–0.27 wt.%; As in pyrite = d.l. to 2.72 wt.%). Samples were collected from active mine faces, and expected differences in the concentration of As in pyrite were confirmed by electron microprobe analysis. Experimental weathering conditions in test chambers were maintained as follows: (1) dry Ar atmosphere; (2) dry O2 atmosphere; (3) room atmosphere (relative humidity ∼20–60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and 57Fe Mössbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. 57Fe Mössbauer spectroscopy also shows a much greater proportion of Fe3+ forms (jarosite, Fe3+ sulfate, FeOOH) for samples stored under wet conditions, but much less

  5. 57 Fe Mössbauer and magnetic studies of Nd3Fe24.5Cr4.5

    NASA Astrophysics Data System (ADS)

    Wang, J. L.; Md Din, M. F.; Campbell, S. J.; Kennedy, S. J.; Yang, F. M.; Wu, G. H.; Dou, S. X.

    2015-04-01

    The structural and magnetic properties of the rare earth transition metal compound Nd 3Fe 24.5Cr 4.5 have been investigated by variable temperature high resolution x-ray diffraction together with DC magnetization and 57Fe Mössbauer effect measurements. The magnetic ordering temperature has been found to be T C= 423(5) K with spin reorientation detected below room temperature around T sr= 158(5) K. Rietveld refinements indicate that Nd 3Fe 24.5Cr 4.5 crystallizes in the Nd 3(Fe,Ti) 29-type structure with the A2/m space group and a substantial magneto-volume effect is detected around T C. The Mössbauer spectra can be fitted well using five sub-spectra. The temperature dependence of the average hyperfine field has been analysed in terms of different power laws of the reduced temperature. The Debye temperature of Nd 3Fe 24.5Cr 4.5 has been determined as 𝜃 D= 400(± 30) K from a fit to the variable temperature isomer shift IS(T).

  6. Study of Vitamins and Dietary Supplements Containing Ferrous Fumarate and Ferrous Sulfate Using Moessbauer Spectroscopy

    SciTech Connect

    Oshtrakh, M. I.; Novikov, E. G.; Semionkin, V. A.; Dubiel, S. M.

    2010-07-13

    A study of several samples of vitamins and dietary supplements containing ferrous fumarate and ferrous sulfate was carried out using Moessbauer spectroscopy with a high velocity resolution. A presence of ferrous and ferric impurities was revealed. Small variations of Moessbauer hyperfine parameters were found for both ferrous fumarates and ferrous sulfates in the investigated medicines.

  7. Thermal decomposition and reconstruction of CaFe-layered double hydroxide studied by X-ray diffractometry and 57Fe Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Bugris, Valéria; Ádok-Sipiczki, Mónika; Anitics, Tamás; Kuzmann, Ernő; Homonnay, Zoltán; Kukovecz, Ákos; Kónya, Zoltán; Sipos, Pál; Pálinkó, István

    2015-06-01

    In spite of numerous investigations on the various processes of the thermal decomposition and rehydration of layered double hydroxides (LDHs) by a variety sophisticated experimental means, many details are still unexplored and some contradictions are still unresolved. In this work, our efforts were focussed on clarifying the composition, structure and properties of thermally decomposed metaphases originating from CaFe-LDH, heat treated in the 373-973 K temperature range. The structure reconstruction ability of mixed metal oxide phases obtained after heat treatments was also investigated, mainly concentrating on the changes in the microenvironment of Fe(III), in the presence of controlled amount of water vapour (i.e., at different relative humidities). All samples were characterised by X-ray diffractometry, and the iron-containing phases were studied by 57Fe Mössbauer spectroscopy.

  8. Multiple superhyperfine fields in a {DyFe2Dy} coordination cluster revealed using bulk susceptibility and (57)Fe Mössbauer studies.

    PubMed

    Peng, Yan; Mereacre, Valeriu; Anson, Christopher E; Powell, Annie K

    2016-08-03

    A [DyFeDy(μ3-OH)2(pmide)2(p-Me-PhCO2)6] coordination cluster, where pmideH2 = N-(2-pyridylmethyl)iminodiethanol, has been synthesized and the magnetic properties studied. The dc magnetic measurements reveal dominant antiferromagnetic interactions between the metal centres. The ac measurements reveal zero-field quantum tunnelling of the magnetisation (QTM) which can be understood, but not adequately modelled, in terms of at least three relaxation processes when appropriate static (dc) fields are applied. To investigate this further, (57)Fe Mössbauer spectroscopy was used and well-resolved nuclear hyperfine structures could be observed, showing that on the Mössbauer time scale, without applied field or else with very small applied fields, the iron nuclei experience three or more superhyperfine fields arising from the slow magnetisation reversal of the strongly polarized fields of the Dy(III) ions.

  9. Mössbauer and X-ray study of biodegradation of 57Fe3 O 4 magnetic nanoparticles in rat brain

    NASA Astrophysics Data System (ADS)

    Gabbasov, R. R.; Cherepanov, V. M.; Chuev, M. A.; Lomov, A. A.; Mischenko, I. N.; Nikitin, M. P.; Polikarpov, M. A.; Panchenko, V. Y.

    2016-12-01

    Biodegradation of a 57Fe3 O 4 - based dextran - stabilized ferrofluid in the ventricular cavities of the rat brain was studied by X-ray diffraction and Mössbauer spectroscopy. A two-step process of biodegradation, consisting of fast disintegration of the initial composite magnetic beads into separate superparamagnetic nanoparticles and subsequent slow dissolution of the nanoparticles has been found. Joint fitting of the couples of Mössbauer spectra measured at different temperatures in the formalism of multi-level relaxation model with one set of fitting parameters, allowed us to measure concentration of exogenous iron in the rat brain as a function of time after the injection of nanoparticles.

  10. Isotopic hybrids of nitrogenase. Mössbauer study of MoFe protein with selective 57Fe enrichment of the P-cluster.

    PubMed

    McLean, P A; Papaefthymiou, V; Orme-Johnson, W H; Münck, E

    1987-09-25

    Previous Mössbauer and EPR studies of the MoFe protein (approximately 30 Fe and 2 Mo) of nitrogenase have revealed the presence of two unique clusters, namely, the P-clusters (presumably of the Fe4S4 type) and the molybdenum- and iron-containing cofactors (or M-clusters). Mössbauer components D (approximately 10-12 Fe) and Fe2+ (approximately 4 Fe) represent subsites of the P-clusters while component S (approximately 2 Fe) appeared to belong to a separate, unidentified cluster. In order to refine the analyses of Mössbauer spectra, we have constructed an isotopic hybrid of the Klebsiella pneumoniae protein which contains 57Fe-enriched P-clusters and 56Fe-enriched M-clusters. The highly resolved 57Fe Mössbauer spectra of this hybrid show that component S behaves spectroscopically like the P-cluster sites D and Fe2+ in oxidized and reduced MoFe protein. This suggests that S is a subset of the P-clusters rather than a different cluster type. The present study shows, for the first time, that the Debye-Waller factors of different P-cluster subsites have a different temperature dependence. Thus, the Fe2+/D absorption ratio is 4.0:10.0 at 4.2 K and 4.0:11.6 at 173 K. We propose that the reduced MoFe protein contains two pairs of P-clusters: one pair containing one Fe2+ and three D-sites and the other one Fe2+, two D, and one S-site. We have argued previously that the oxidized P-clusters occur in pairs as well.

  11. The 57Fe hyperfine interactions in iron storage proteins in liver and spleen tissues from normal human and two patients with mantle cell lymphoma and acute myeloid leukemia: a Mössbauer effect study

    NASA Astrophysics Data System (ADS)

    Oshtrakh, M. I.; Alenkina, I. V.; Vinogradov, A. V.; Konstantinova, T. S.; Semionkin, V. A.

    2015-04-01

    Study of human spleen and liver tissues from healthy persons and two patients with mantle cell lymphoma and acute myeloid leukemia was carried out using Mössbauer spectroscopy with a high velocity resolution. Small variations in the 57Fe hyperfine parameters for normal and patient's tissues were detected and related to small variations in the 57Fe local microenvironment in ferrihydrite cores. The differences in the relative parts of more crystalline and more amorphous core regions were also supposed for iron storage proteins in normal and patients' spleen and liver tissues.

  12. Designing and characterization of Fe(III) complexes of oxydiacetate containing α-diimine as auxiliary ligand: 57Fe-Mössbauer and cyclic voltammetric studies

    NASA Astrophysics Data System (ADS)

    Shahid, M.; Sharma, Prashant K.; Siddiqi, Zafar A.; Sama, Farasha; Ansari, Istikhar A.; Khalid, Mohd.

    2014-04-01

    The newly prepared complexes with stoichiometries [Fe(oda)(phen)Cl] (1), [Fe(oda)(4-picNO)(H2O)Cl)] (2) and [Fe2(oda)2(H2O)2Cl2] (3) [H2oda = oxydiacetic acid, phen = 1,10‧-phenantroline and 4-picNO = 4-picoline-N-oxide] were synthesized under varying experimental conditions. The complexes were characterized by spectral (IR, FAB-MS and Mössbauer), electrochemical and thermal studies. 57Fe-Mössbauer spectral data for complexes exhibit a quadrupole splitting confirming the presence of iron nuclei in asymmetric environment. The relevant parameters like isomer shift (δ), quadruple splitting (ΔEQ), line widths and peak height ratio (HWh/HWl) are consistent with high spin state of Fe(III) centre with the presence of Kramer’s double degeneracy in distorted octahedral environment. The electrochemical studies indicate existence of quasi-reversible redox couples (FeII/III) in solution.

  13. Magnetic and 57Fe Mössbauer study of the single molecule magnet behavior of a Dy3Fe7 coordination cluster.

    PubMed

    Abbas, Ghulam; Lan, Yanhua; Mereacre, Valeriu; Wernsdorfer, Wolfgang; Clérac, Rodolphe; Buth, Gernot; Sougrati, Moulay T; Grandjean, Fernande; Long, Gary J; Anson, Christopher E; Powell, Annie K

    2009-10-05

    The reaction between N-methydiethanolamine (mdeaH(2)), benzoic acid, FeCl(3), and DyCl(3) yields a decanuclear coordination cluster, [Dy(3)Fe(7)(mu(4)-O)(2)(mu(3)-OH)(2)(mdea)(7)(mu-benzoate)(4)(N(3))(6)] x 2 H(2)O x 7 CH(3)OH (1) whose single crystal structure exhibits three and seven crystallographically distinct Dy(III) and Fe(III) ions; six of the Fe(III) ions are pseudo-octahedrally coordinated, whereas the seventh has a trigonal-bipyramidal coordination geometry. Both direct current (dc) and alternating current (ac) magnetic susceptibility studies indicate that, upon cooling, intracluster antiferromagnetic interactions are dominant in 1, yielding a ferrimagnetic spin arrangement. The out-of-phase (chi'') ac susceptibility reveals that 1 undergoes a slow relaxation of its magnetization mainly resulting from the anisotropy of the Dy(III) ions. This slow relaxation has been confirmed both by magnetization measurements on an oriented single crystal of 1 and by the observation of hysteresis loops below 1.9 K. The macroscopic magnetic studies yield an effective energy barrier, U(eff), of 33.4 K for this relaxation, a barrier that is the highest yet reported for a lanthanide(III)-Fe(III) single molecule magnet. The (57)Fe Mössbauer spectra of 1 obtained between 3 and 35 K are consistent with the presence of Fe(III) intracluster antiferromagnetic coupling with slow magnetic relaxation relative to the Larmor precession time, thus confirming, on a microscopic scale, the presence of a barrier to the magnetic relaxation below 35 K. Between 55 and 295 K the Mössbauer spectra reveal paramagnetic behavior with six partially resolved quadrupole doublets, one for the trigonal-bipyramidal Fe(III) site and five for the six pseudo-octahedral Fe(III) sites.

  14. Moessbauer study of iron redox in West Valley glass

    SciTech Connect

    Yaschenko, E.; Salahuddin, H.; Muller, I.S.; Pegg, I.L.; Macedo, P.B.

    1994-12-31

    High-level nuclear wastes at West Valley are high in iron which results in a target glass composition for the vitrification process that contains about 12 wt% Fe{sub 2}O{sub 3}. We have developed a series of high-iron glass formulations (up to 21 wt% Fe{sub 2}O{sub 3}) in order to accommodate all reasonable waste stream variability. An additional process control variable is the glass redox ratio, Fe{sup 2+}/(Fe{sup 2+}+Fe{sup 3+}), since this affects the resultant glass properties including durability, crystallization, glass transition temperature, and melt viscosity. In this study, a range of redox states was obtained by bubbling CO/CO{sub 2} mixtures through the melts. The redox state was determined by Moessbauer spectroscopy and correlations between redox state and CO/CO{sub 2} ratio, flow rate, and time were obtained. Analysis of the spectroscopic data provides additional information on changes in the occupation of tetrahedral and octahedral sites with redox state.

  15. SEM, optical, and Moessbauer studies of submicrometer chromite in Allende

    NASA Technical Reports Server (NTRS)

    Housley, R. M.

    1982-01-01

    New scanning electron and optical microscope results are presented showing that sub-micrometer chromite is abundant along healed cracks and grain boundaries in Allende chondrule olivine. Some wider healed cracks also contain pentlandite and euhedral Ni3Fe grains. Also reported are Moessbauer measurements on Allende HF-HCl residues confirming a high Fe(+++)/Fe(++) ratio.

  16. Thermal Transformations of Iron Cations in the System Metal-Vitreous Enamel Coat. Moessbauer Spectroscopic Study

    SciTech Connect

    Barcova, K.; Mashlan, M.; Zboril, R.; Hrabovska, K.

    2005-04-26

    Vitreous enameling on steel is carried out to provide a protective layer against chemical corrosion from the surrounding environment. The glass bonds with the steel to form a composite material. The Moessbauer spectroscopy was firstly applied to study the vitreous enameling in which the complex of processes, as diffusion of species, adhesion between the glass and the steel, galvanic reactions, plays an important role. The Moessbauer spectroscopy provides unique information about the Fe-phase structure of the vitreous enamel layer and that of the steel-enamel interface. Diffusion of iron from steel surface towards enamel layer and formation of a new Fe2+ phase was proved.

  17. Moessbauer Study of Sphero-Conical Vessels from Bolgar

    NASA Astrophysics Data System (ADS)

    Ivanova, A. G.; Nuretdinova, A. R.; Pyataev, A. V.; Valiulina, S. I.; Voronina, E. V.

    2017-05-01

    Samples of sphero-conical vessels found in mass quantities in the ancient settlement Bolgar were analyzed by Moessbauer spectroscopy. Wares with relatively low annealing temperatures <500°C and having a ratio Fepar/Fe2+ ≤ 1.11 in transmission spectra were differentiated from those with high ones. The detected value of {Fe}_{par}^{3+} /Fe2+ was considerably less than the value of 2.69 that was characteristic of raw materials for pottery production in the vicinity of the selected settlement. This indicated that other non-local sources of raw materials existed in the medieval handicraft center.

  18. Antiferromagnetism in Co-57-doped La2CuO(4-y) studied by Moessbauer spectroscopy

    NASA Technical Reports Server (NTRS)

    Jha, S.; Mitros, C.; Lahamer, Amer; Yehia, Sherif; Julian, Glenn M.

    1989-01-01

    Moessbauer effect studies of Co-57-doped La2CuO(4-y) were performed at temperatures between 4.2 K and room temperature. These confirm the antiferromagnetic ordering of these compounds below room temperature. Temperature dependence of the quadrupole splitting shows that the hyperfine field is at an angle with the c-axis.

  19. Moessbauer study in thin films of FeSi2 and FeSe systems

    NASA Technical Reports Server (NTRS)

    Escue, W. J.; Aggarwal, K.; Mendiratta, R. G.

    1978-01-01

    Thin films of FeSi2 and FeSe were studied using Moessbauer spectroscopy information regarding dangling bond configuration and nature of crystal structure in thin films was derived. A significant influence of crystalline aluminum substrate on film structure was observed.

  20. Use of Moessbauer spectroscopy to study reaction products of polyphenols and iron compounds

    SciTech Connect

    Gust, J. ); Suwalski, J. )

    1994-05-01

    Moessbauer spectroscopy was used to study parameters of the reaction products of iron compounds (Fe[sup III]) and polyphenols with hydroxyl (OH) groups in ortho positions. Polyphenols used in the reaction were catechol, pyrogallol, gallic acid, and oak tannin. The Fe-containing compounds were hydrated ferric sulfate (Fe[sub 2][SO[sub 4

  1. /sup 57/Fe Mossbauer spectroscopy of U/sub 6/Fe

    SciTech Connect

    Lemon, G.; Boolchand, P.; Stevens, M.; DeLong, L.E.; Huber, J.G.; Marcuso, M.

    1986-04-01

    Samples of U/sub 6/Fe were prepared by arc melting U and enriched /sup 57/Fe. The samples display superconducting transitions which are sensitive to long-term exposure to air. Room temperature spectra of U/sub 6/Fe typically display a majority site A (quadrupole splitting ..delta.. = 0.749(3) mm/s, isomer shift delta = 0.482(6) mm/s relative to Cu) and a minority site B (..delta.. = 0.55(3) mm/s, sigma = 0.12(3) mm/s) with the site intensity ratio (I/sub B//I/sub A/) typically 0.05 to 0.10. The I/sub B//I/sub A/ intensity ratio increases upon air exposure of the samples. We have studied Moessbauer spectra as a function of temperature T in the range 15/sup 0/K less than or equal to T less than or equal to 310/sup 0/K paying particular attention to the T-variation of the isomer-shift and recoil-free-fraction of the majority site A. Results indicate a consistent softening of lattice vibrations of U/sub 6/Fe at T approx. = 170/sup 0/K.

  2. High perfection. alpha. - sup 57 Fe sub 2 O sub 3 crystals for nuclear Bragg scattering

    SciTech Connect

    Suzuki, C.K.; Ohno, H. ); Takei, H.; Sakai, F. ); Yoda, Y.; Kudo, Y.; Izumi, K.; Ishikawa, T.; Kikuta, S. ); Zhang, X.W.; Matsushita, T.; Ando, M. )

    1992-01-01

    High quality single crystals or thin films containing Moessbauer isotopes are the main x-ray optical component for nuclear Bragg scattering (NBS) with synchrotron radiation. For this purpose, flux grown {alpha}-{sup 57}Fe{sub 2}O{sub 3} (hematite) single crystals prepared in two growth runs have been characterized by plane wave x-ray topography, which indicated the most suitable sample. Measurements of (111), (333), (555), (777), and (999) pure nuclear-reflection profiles showed a good agreement of relative reflectivity with the values calculated from theory. At the beamline NE-3, accumulation ring of TRISTAN, a Moessbauer event rate as high as 13 000 cps for (777) reflection was observed.

  3. Interplay between magnetism and superconductivity in EuFe2-xCoxAs2 studied by 57Fe and 151Eu Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Błachowski, A.; Ruebenbauer, K.; Żukrowski, J.; Bukowski, Z.; Rogacki, K.; Moll, P. J. W.; Karpinski, J.

    2011-11-01

    The compound EuFe2-xCoxAs2 was investigated by means of 57Fe and 151Eu Mössbauer spectroscopy versus temperature (4.2-300 K) for x = 0 (parent), x = 0.34-0.39 (superconductor), and x = 0.58 (overdoped). It was found that the spin density wave (SDW) is suppressed by Co substitution; however, it survives in the region of superconductivity, but iron spectra exhibit some nonmagnetic components in the superconducting region. Europium orders magnetically, regardless of the cobalt concentration, with the spin reorientation from the a-axis in the parent compound toward the c-axis with increasing replacement of iron by cobalt. The reorientation takes place close to the a-c plane. Some trivalent europium appears in EuFe2-xCoxAs2 versus substitution due to the chemical pressure induced by Co atoms, and it experiences some transferred hyperfine field from Eu2+. Iron experiences some transferred field due to the europium ordering for substituted samples in the SDW and nonmagnetic state both, while the transferred field is undetectable in the parent compound. Superconductivity coexists with the 4f-europium magnetic order within the same volume. It seems that superconductivity has some filamentary character in EuFe2-xCoxAs2, and it is confined to the nonmagnetic component seen by the iron Mössbauer spectroscopy.

  4. Bulk and thin films of FeTe: A Moessbauer study

    NASA Technical Reports Server (NTRS)

    Escue, W. T.; Aggarwal, K.; Mendiratta, R. G.

    1977-01-01

    Studies of bulk and thin films of FeTe using Moessbauer spectroscopy showed that FeTe has one noncubic Fe (+2) site which is 3d2 4s 4p3 hybridized. The presence of dangling bands was indicated in spectra of FeTe thin films. The films showed a tendency of texture formation. The substrate was observed to influence the film structure and nature of bonds in films.

  5. Moessbauer and adhesion study of ion beam-modified Fe-PTFE interfaces

    NASA Astrophysics Data System (ADS)

    Ingemarsson, P. Anders; Ericsson, Tore; Wappling, Roger; Possnert, Goran

    Conversion electron Moessbauer spectroscopy was used to study ion beam-induced effects at Fe-PTFE thin film interfaces and to relate these effects to accompanying modifications in adhesion. Irradiation with 16 MeV S-32(3+) ions to doses in the range between 5 x 10 to the 11th and 2 x 10 to the 14th ions/sq cm was carried out before or after deposition of thin Fe-57 layers. For both pre- and post-bombardment, a substantial adhesion enhancement was observed. Associated with this were significant changes in the Moessbauer spectra indicating the formation of Fe-C and Fe-F compounds. This compound formation can be associated with the observed improvement in thin film adhesion.

  6. Novel iron complexes bearing N6-substituted adenosine derivatives: synthesis, magnetic, 57Fe Mössbauer, DFT, and in vitro cytotoxicity studies.

    PubMed

    Trávnícek, Zdenek; Mikulík, Jirí; Cajan, Michal; Zboril, Radek; Popa, Igor

    2008-09-15

    Iron complexes (1-7) involving N6-benzyladenosine derivatives of the predominant composition [Fe(L(n))Cl(3)].H(2)O {where L(1)=N6-(2-fluorobenzyl)adenosine (1), L(2)=N6-(4-fluorobenzyl)adenosine (2), L(3)=N6-(2-trifluoromethylbenzyl)adenosine (3), L(4)=N6-(3-trifluoromethylbenzyl)adenosine (4), L(5)=N6-(4-trifluoromethylbenzyl)adenosine (5), L(6)=N6-(4-trifluoromethoxybenzyl)adenosine (6), and L(7)=N6-(4-chlorobenzyl)adenosine (7)} have been synthesized. The compounds have been characterized by elemental analysis, variable-temperature and in-field 57Fe Mössbauer, ES+ MS, FTIR, 1H and 13C NMR spectroscopies, magnetochemical and conductivity measurements, thermal (TGA/DSC/DTA) analyses, and DFT calculations. It has been found that the organic molecule is coordinated to iron via N7 atom of the appropriate adenosine derivative and the products are represented by mixtures of complexes with various iron oxidation (Fe(III)/Fe(II)) and spin states (S=5/2, 4/2, 3/2, 2/2) and geometries (tetrahedral or trigonal bipyramidal). It is caused by the fact that partial redox processes proceed during the reactions due to the presence of a ribose moiety, which is oxidized to the corresponding 5'-ribotic acid, and simultaneously, a portion of Fe(III) cations is reduced to Fe(II) ones. Moreover, a significant effect of crystal water molecules on stereochemistry, and hence, on magnetic and spectral properties of the prepared complexes has been found. The compounds have been tested for their in vitro cytotoxicity against the following human cancer cell lines: malignant melanoma (G-361), osteogenic sarcoma (HOS), chronic myelogenous leukemia (K-562), and breast adenocarcinoma (MCF-7). The most important results have been obtained for complex 2 with IC(50) values 8-16 microM against HOS, K-562, and MCF-7 cell lines, and for complex 6 with IC(50) value 4 microM against MCF-7 cell line.

  7. Mössbauer study of exogenous iron redistribution between the brain and the liver after administration of 57Fe3O4 ferrofluid in the ventricle of the rat brain

    NASA Astrophysics Data System (ADS)

    Polikarpov, Dmitry; Gabbasov, Raul; Cherepanov, Valery; Loginova, Natalia; Loseva, Elena; Nikitin, Maxim; Yurenia, Anton; Panchenko, Vladislav

    2015-04-01

    Iron clearance pathways after the injection of 57Fe3O4-based ferrofluid into the brain ventricles were studied histologically and by Mössbauer spectroscopy. It was found that the dextran coated initial nanobeads of the ferrofluid disintegrated in the brain into separate superparamagnetic nanoparticles within a week after the injection. The exogenous iron completely exited all ventricular cavities of the brain within a week after the injection but remained in the white matter for months. Kupffer cells with the exogenous iron appeared in the rat liver 2 hours after the injection. Their concentration reached its maximum on the third day and dropped to zero within a week. The exogenous iron appeared in the spleen a week after the injection and remained in the spleen for months.

  8. Structure, phase transitions, 55Mn NMR, 57Fe Mössbauer studies and magnetoresistive properties of La0.6Sr0.3Mn1.1-xFexO3

    NASA Astrophysics Data System (ADS)

    Pashchenko, A. V.; Pashchenko, V. P.; Revenko, Yu. F.; Prokopenko, V. K.; Shemyakov, A. A.; Levchenko, G. G.; Pismenova, N. E.; Kitaev, V. V.; Gufan, Yu. M.; Sil'cheva, A. G.; Dyakonov, V. P.

    2014-11-01

    The influence of substitution of Fe ions for manganese on the structure, phase transitions, magnetoresistance, 55Mn NMR and 57Fe Mössbauer spectra in the ceramic La0.6Sr0.3Mn1.1-xFexO3 (x=0-0.15) samples has been studied by X-ray diffraction, electron microscopy, magnetic, 55Mn NMR and 57Fe Mössbauer methods. The real rhombohedral perovskite structure (R3barc) is established to contain the different valence manganese ions (Mn3+ and Mn4+), anion and cation vacancies as well as nanostructural clusters with Mn2+ located in the A-sites. Temperature dependences of the a lattice parameter, a(T), demonstrate the anomalies near the Curie temperature, Tc. Wide asymmetric 55Mn NMR spectra confirm the high frequency electron double exchange between Mn3+ and Mn4+ ions and irregularity of their surrounding by other ions and defects. According to the Mössbauer spectroscopy data, Fe3+ ions (~80%) substitute for Mn3+ and partially Mn4+ in the B-positions. The rest of Fe3+ (Fe2+) ions and clusters with Mn2+ are located in the A-positions. The temperatures of metal-semiconductor and ferromagnet-paramagnet phase transitions are reduced with increasing x, and the magnetic irregularity increases due to the weakening high-frequency Mn3+↔Mn4+ double exchange by Fe3+ ions. The amount of ferromagnetic phase is also reduced. The anomalous hysteresis is interpreted as a result of anisotropy of exchange interaction between the ferromagnetic matrix and antiferromagnetic cluster containing MnA2+ ions. The phase diagram demonstrates the strong correlated interrelation among magnetic, transport and magnetoresistance properties.

  9. Moessbauer studies of exchange-coupled two-iron centers in proteins

    SciTech Connect

    Sage, J.T.

    1986-01-01

    This study reports Moessbauer measurements on three derivatives of the oxygen-transport protein hemerythrin and on the oxidized and reduced forms of uteroferrin, a purple acid phosphatase isolated from porcine uterine fluid. Both proteins contain an exchange-coupled pair of iron atoms coordinated directly to amino acid side chains. A model that takes account of both the exchange coupling and the zero-field splitting at each site is presented and used to describe the magnetic properties of the ground spin multiplet of a pair of coupled spins. One notable feature of the model is the fact that the g- and A-tensors of the coupled system may be quite anisotropic even if the corresponding single-site tensors are not. Preliminary studies of some non-Kramers systems are also presented. The Moessbauer spectrum of an azide derivative of deoxyhemerythrin broadens in a small applied field, indicating the presence of a near degeneracy. The spectrum of oxidized uteroferrin broadens as the temperature is raised, even in the absence of an applied field. No fully adequate explanation for the latter observation is apparent.

  10. Interfacial magnetism of Ce/Fe and CeH ˜2/Fe multilayers studied by 57Fe Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Bauer, Ph.; Klose, F.; Schulte, O.; Felsch, W.

    1994-11-01

    The distribution of the magnetic hyperfine fields and the magnetic anisotropy of Ce/Fe and CeH ˜2/Fe multilayers have been studied by Mössbauer spectroscopy between 4.2 and 300 K. The extension of the Ce-Fe interaction defining a 'magnetic interface' exceeds the structural extension of the interface and is more than two times larger at the Ce/Fe than at the CeH ˜2/Fe interface. This is proposed to be a consequence of a strong hybridization between the Ce-5d and Fe-3d states that is suppressed by hydrogenation. From the relative intensity of the Mössbauer lines we show that for the CeH ˜2/Fe system with sufficiently thin Fe layers the orientation of the spontaneous magnetization is perpendicular to the film plane at low temperatures and switches to a parallel alignment at higher temperatures in a sharp transition. In contrast, the Ce/Fe system is spontaneously magnetized in the film plane.

  11. Origin of Tc Enhancement Induced by Doping Yttrium and Hydrogen into LaFeAsO-Based Superconductors: 57Fe-, 75As-, 139La-, and 1H-NMR Studies

    NASA Astrophysics Data System (ADS)

    Yamashita, Hiroki; Mukuda, Hidekazu; Yashima, Mitsuharu; Furukawa, Satoshi; Kitaoka, Yoshio; Miyazawa, Kiichi; Shirage, Parasharam M.; Eisaki, Hiroshi; Iyo, Akira

    2010-10-01

    We report our extensive 57Fe-, 75As-, 139La-, and 1H-NMR studies of La0.8Y0.2FeAsO1-y (La0.8Y0.21111) and LaFeAsO1-yHx (La1111H), where doping yttrium (Y) and hydrogen (H) into optimally doped LaFeAsO1-y [La1111(OPT)] increases Tc=28 to 34 and 32 K, respectively. In the superconducting (SC) state, the measurements of nuclear-spin lattice-relaxation rate 1/T1 have revealed in terms of a multiple fully gapped s±-wave model that the SC gap and Tc in La0.8Y0.21111 become larger than those in La1111(OPT) without any change in doping level. In La1111H, the SC gap and Tc also increase slightly even though a decrease in carrier density and some disorders are significantly introduced. As a consequence, we suggest that the optimization of both the structural parameters and the carrier doping level to fill up the bands is crucial for increasing Tc among these La1111-based compounds through the optimization of the Fermi surface topology.

  12. Moessbauer study of amorphous (FeTM){sub 80}B{sub 20}

    SciTech Connect

    Orue, I.; Plazaola, F.; Fernandez-Gubieda, M.L.; Gutierrez, J.; Barandiaran, J.M.

    1994-03-01

    As-cast ferromagnetic amorphous alloys of nominal composition (FeTM){sub 80}B{sub 20} have been studied by Moessbauer Spectroscopy, being TM one transition metal atom, Ni, Cr, Mo or Pd. A detailed analysis of the isomer shift, IS, and hyperfine field distribution, HFD, at Fe sites is reported in order to achieve some conclusions about the Chemical Short Range Order and the electronic structure in these alloys. HFD changes found in (FeNi)B for Ni rich concentrations suggest the existence of Fe atoms strongly interacting with Ni. Small amounts of Cr and Mo shift the HFD to lower values of hyperfine field, B{sub hf}, while Pd enhances the B{sub hf}.

  13. The 57Fe hyperfine interactions in the iron-bearing phases in some LL ordinary chondrites

    NASA Astrophysics Data System (ADS)

    Oshtrakh, M. I.; Maksimova, A. A.; Grokhovsky, V. I.; Petrova, E. V.; Semionkin, V. A.

    2016-12-01

    The study of several LL ordinary chondrites such as NWA 6286 LL6, NWA 7857 LL6 and Chelyabinsk LL5 fragments with different lithology was carried out using scanning electron microscopy with energy dispersion spectroscopy, X-ray diffraction and 57Fe Mössbauer spectroscopy with a high velocity resolution at 295 K. Small variations in the 57Fe hyperfine parameters were revealed for the M1 and M2 sites in olivine, orthopyroxene and clinopyroxene as well as for α-Fe(Ni, Co), α 2-Fe(Ni, Co) and γ-Fe(Ni, Co) phases, and for troilite in different samples of studied LL ordinary chondrites.

  14. Determination of the Lamb-Moessbauer factors of LiFePO{sub 4} and FePO{sub 4} for electrochemical in situ and operando measurements in Li-ion batteries

    SciTech Connect

    Aldon, L.

    2010-01-15

    {sup 57}Fe Moessbauer spectroscopy is a powerful tool to investigate redox reactions during in electrochemical lithium insertion/extraction processes. Electrochemical oxidation of LiFe{sup II}PO{sub 4} (triphylite) in Li-ion batteries results in Fe{sup III}PO{sub 4} (heterosite). LiFePO{sub 4} was synthesized by solid state reaction at 800 deg. C under Ar flow from Li{sub 2}CO{sub 3}, FeC{sub 2}O{sub 4}.2H{sub 2}O and NH{sub 4}H{sub 2}PO{sub 4} precursors in stoichiometric composition. FePO{sub 4} was prepared from chemical oxidation of LiFePO{sub 4} using bromine as oxidative agent. For both materials a complete {sup 57}Fe Moessbauer study as a function of the temperature has been carried out. The Debye temperatures are found to be theta{sub M}=336 K for LiFePO{sub 4} and theta{sub M}=359 K for FePO{sub 4}, leading to Lamb-Moessbauer factors f{sub 300K}=0.73 and 0.77, respectively. These data will be useful for a precise estimation of the relative amounts of each species in a mixture. - Graphical abstract: Relative amount of FePO{sub 4} obtained by Moessbauer and electrochemical data. We have corrected Moessbauer spectral intensities with our f factor of both LiFePO{sub 4} and FePO{sub 4}. Open (filled) squares correspond to values obtained during charging (discharging) process. The dashed line, given as a guideline for the eye, corresponds to the ideal case were amounts deduced from different experimental measurements are equal.

  15. Moessbauer spectroscopy study on the corrosion resistance of plasma nitrided ASTM F138 stainless steel in chloride solution

    SciTech Connect

    Souza, S.D. de; Olzon-Dionysio, M.; Basso, R.L.O.; Souza, S. de

    2010-10-15

    Plasma nitriding of ASTM F138 stainless steel samples has been carried out using dc glow discharge under 80% H{sub 2}-20% N{sub 2} gas mixture, at 673 K, and 2, 4, and 7 h time intervals, in order to investigate the influence of treatment time on the microstructure and the corrosion resistance properties. The samples were characterized by scanning electron microscopy, glancing angle X-ray diffraction and conversion electron Moessbauer spectroscopy, besides electrochemical tests in NaCl aerated solution. A modified layer of about 6 {mu}m was observed for all the nitrided samples, independent of nitriding time. The X-ray diffraction analysis shows broad {gamma}{sub N} phase peaks, signifying a great degree of nitrogen supersaturation. Besides {gamma}{sub N,} the Moessbauer spectroscopy results indicated the occurrence of {gamma}' and {epsilon} phases, as well as some other less important phases. Corrosion measurements demonstrate that the plasma nitriding time affects the corrosion resistance and the best performance is reached at 4 h treatment. It seems that the {epsilon}/{gamma}' fraction ratio plays an important role on the resistance corrosion. Additionally, the Moessbauer spectroscopy was decisive in this study, since it was able to identify and quantify the iron phases that influence the corrosion resistance of plasma nitrided ASTM F138 samples.

  16. Moessbauer and Electron Microprobe Studies of Density Separates of Martian Nakhlite Mil03346: Implications for Interpretation of Moessbauer Spectra Acquired by the Mars Exploration Rovers

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; McKay, G. A.; Agresti, D. G.; Li, Loan

    2008-01-01

    Martian meteorite MIL03346 is described as an augite-rich cumulate rock with approx.80%, approx.3%, and approx.21% modal phase proportions of augite (CPX), olivine and glassy mesostasis, respectively, and is classified as a nakhlite [1]. The Mossbauer spectrum for whole rock (WR) MIL 03346 is unusual for Martian meteorites in that it has a distinct magnetite subspectrum (7% subspectral area) [2]. The meteorite also has products of pre-terrestrial aqueous alteration ("iddingsite") that is associated primarily with the basaltic glass and olivine. The Mossbauer spectrometers on the Mars Exploration Rovers have measured the Fe oxidation state and the Fe mineralogical composition of rocks and soils on the planet s surface since their landing in Gusev Crater and Meridiani Planum in January, 2004 [3,4]. The MIL 03346 meteorite provides an opportunity to "ground truth" or refine Fe phase identifications. This is particularly the case for the so-called "nanophase ferric oxide" (npOx) component. NpOx is a generic name for a ferric rich product of oxidative alteration. On Earth, where we can take samples apart and study individual phases, examples of npOx include ferrihydrite, schwertmannite, akagaaneite, and superparamagnetic (small particle) goethite and hematite. It is also possible for ferric iron to be associated to some unknown extent with igneous phases like pyroxene. We report here an electron microprobe (EMPA) and Moessbauer (MB) study of density separates of MIL 03346. The same separates were used for isotopic studies by [5]. Experimental techniques are described by [6,7].

  17. Moessbauer studies of rare earth-iron hydrides, carbides, and nitrides

    SciTech Connect

    Ryan, D.H.; Chen, X.; Altounian, Z. )

    1993-04-01

    The basic principles of Moessbauer spectroscopy are introduced in the context of magnetically ordered alloys. A description of fitting procedures is presented, emphasizing the use of information derived from other techniques and indicating reliability limits. Ways in which the local structural and magnetic information obtained from Moessbauer spectroscopy can be used to probe the effects of hydrogen, carbon, and nitrogen additions in R2Fe17 alloys are presented, as well as how to distinguish local and global changes. Even apparently large-scale effects, such as change in the magnetic easy direction, are shown to have clear local signatures. A new hybrid carbonitride of the 2-17 alloy series is introduced, which combines superior magnetic properties with enhanced thermal stability. The coherent two-phase structure of this material, revealed by Moessbauer spectroscopy, is used to emphasize the different information obtained from local and bulk measurements.

  18. Studies in Moessbauer spectroscopy, neutron activation analysis, x-ray fluorescence

    SciTech Connect

    Nomai, M.

    1985-01-01

    The Moessbauer Effects was employed to study cyclopentadienyliron arene compounds. The isomer shift, delta, in these compounds ranges from 0.206 to 0.257 mm/s relative to /sup 5//sub 7/Co/Cu source and ..delta..E/sub Q/ values are from 1.632 to 1.918 mm/s at liquid nitrogen temperature. Room temperature spectra showed low absorption due to small recoil-free fractions the deltas and ..delta..E/sub Q/s can be correlated with the electron withdrawing effects of the alkyl groups bonded to benzene. In polynuclear aromatic system extending over two benzene rings, electron charge density is difficult to explain. Isomer shifts of PF/sub 6//sup -/ and Fe(NCS)/sub 6//sup 3 -/ are more or less independent of the counteranion, while ..delta..E/sub Q/ is slightly influenced by it. (Fe(arene)Cp)/sub 3//sup +/FE(NCS)/sub 6//sup 3 -/ compounds show only two peaks, with parameters almost identical to the PF/sub 6//sup -/ compounds. An isomer shift peak due to Fe(NCS)/sub 6//sup 3 -/, Fe d/sup 5/ state, is not observed and it is believed to coincide with the second right hand peak of the cation. Experimental procedures and results of hydrogen determination in samples of coal and other comparative samples, e.g., NA/sub 2/EDTA.2H/sub 2/O, in a paraffin moderated thermal neutron flux from 1 ..mu..Ci of /sup 252/Cf source are described. Simple instrumentation is used. Accuracy of about 10% or better is possible with stronger neutron source. Other moderators that were tried, but were unsuccessful, were water and graphite. Factors that can affect the neutron flux and prompt ..gamma..-ray distribution in the samples are H, O, and C concentrations. Results of the determination of uranium and other elements in sandstone uranium samples from Zambia are presented.

  19. Moessbauer study of iron-carbide growth and Fischer-Tropsch activity

    SciTech Connect

    Rao, K.R.P.M.; Huggins, F.E.; Huffman, G.P.

    1995-12-31

    There is a need to establish a correlation between the Fischer-Tropsch (FT) activity of an iron-based catalyst and the catalyst phase during FT synthesis. The nature of iron phases formed during activation and FT synthesis is influenced by the gas used for activation. Moessbauer investigations of iron-based catalysts subjected to pretreatment in gas atmospheres containing mixtures of CO, H{sub 2}, and He have been carried out. Studies on UCI 1185-57 catalyst indicate that activation of the catalyst in CO leads to the formation of 100% magnetite and the magnetite formed gets rapidly converted to at least 90% of x-Fe{sub 5}C{sub 2} during activation. The x-Fe{sub 5}C{sub 2} formed during activation gets partly (= 25%) converted back to Fe{sub 3}O{sub 4} during FT synthesis and both x-Fe{sub 5}C{sub 2} and Fe{sub 3}O{sub 4} reach constant values. On the other hand, activation of the catalyst in synthesis gas leads to formation of Fe{sub 3}O{sub 4} and which is slowly converted to x-Fe{sub 5}C{sub 2} and e-Fe{sub 2.2}C during activation, and both carbide phases increase slowly during FT synthesis. FT synthesis activity is found to give rise to {approx} 70% (H2+CO) conversion in the case of CO activated catalyst as compared to {approx} 20% (H2+CO) conversion in the case of synthesis gas-activated catalyst.

  20. Internal friction and Moessbauer study of C{endash}Cr associates in MANET steel

    SciTech Connect

    Gondi, P.; Gupta, R.; Montanari, R.; Principi, G.; Tata, M.E.

    1997-02-01

    Internal friction and Moessbauer techniques have been used to investigate the structure of C{endash}Cr associates and the arrangement of Fe atoms near them in the Cr martensitic steel MANET subjected to different thermal treatments. After slow rate cooling from the austenitic field, the Moessbauer spectra exhibit, besides the complex magnetic pattern of martensite, a low intensity single attributed to the presence of a Cr-rich b.c.c. phase. In correspondence, the internal friction curves show, among others, a Snoek-type peak due to an elastic processes involving C{endash}Cr associates with 6 Cr atoms. To explain the experimental results a simple structure model is suggested. {copyright} {ital 1997 Materials Research Society.}

  1. 57Fe Mössbauer measurements and electronic structure calculations on natural lawsonites

    NASA Astrophysics Data System (ADS)

    Weber, S.-U.; Grodzicki, M.; Geiger, C. A.; Lottermoser, W.; Tippelt, G.; Redhammer, G. J.; Bernroider, M.; Amthauer, G.

    2007-01-01

    Three natural lawsonites from Syke Rock, Mendocino Co., Reed Ranch, Marin Co., and Blake Gardens, Sonoma Co., all from the Coast Range Region in California, were studied by 57Fe Mössbauer spectroscopy, electron microprobe analysis, and X-ray powder diffraction. The samples contain about 0.6, 1.0, and 1.4 wt% of total iron oxide, respectively. 57Fe Mössbauer spectra are consistent with the assumption that high-spin Fe3+ substitutes for Al in the octahedrally coordinated site. The Mössbauer spectrum of lawsonite from Syke Rock exhibits a second doublet with 57Fe hyperfine parameters typical for octahedrally coordinated high-spin Fe2+. Electronic structure calculations in the local spin density approximation yield quadrupole splittings for Fe3+ in quantitative agreement with experiment indicating, however, that substitution of Al by Fe3+ must be accompanied by local distortion around the octahedral site. Model calculations also reproduce the room temperature hyperfine parameters of ferrous high-spin iron assuming the substitution of Ca by Fe2+. However, it cannot be excluded that Fe2+ may occupy a more asymmetric site within the microstructural cavity occupied by Ca and a H2O molecule.

  2. Moessbauer study of iron-carbide growth and Fischer-Tropsch activity

    SciTech Connect

    Rao, K.R.P.M.; Huggins, F.E.; Huffman, G.P.

    1995-12-31

    There is a need to establish a correlation between the Fischer-Tropsch (FT) activity of an iron-based catalyst and the catalyst phase during FT synthesis. The nature of iron phases formed during activation and FT synthesis is influenced by the nature of the gas and pressure apart from other parameters like temperature, flow rate etc., used for activation. Moessbauer investigations of iron-based catalysts subjected to pretreatment at two different pressures in gas atmospheres containing mixtures of CO, H{sub 2}, and He have been carried out. Studies on UCI 1185-57 (64%Fe{sub 2}O{sub 3}/5%CuO/1%K{sub 2}O/30% Kaolin) catalyst indicate that activation of the catalyst in CO at 12 atms. leads to the formation of 100% magnetite and the magnetite formed gets rapidly converted to at least 90% of {chi}-Fe{sub 5}C{sub 2} during activation. The FT activity was found to be good at 70-80% of (H{sub 2}+CO) conversion. On the other hand, activation. The FT activity was found to be good at 70-80% of (H{sub 2}+CO) conversion. On the other hand, activation of the catalyst in synthesis gas at 12 atms. leads to formation of Fe{sub 3}O{sub 4} and it gets sluggishly converted to {chi}-Fe{sub 5}C{sub 2} and {epsilon}-Fe{sub 2.2}C during activation and both continue to grow slowly during FT synthesis. FT activity is found to be poor. Pretreatment of the catalyst, 100fe/3.6Si/0.71K at a low pressure of 1 atms. in syngas gave rise to the formation of {chi}-Fe{sub 5}C{sub 2} and good FT activity. On the other hand, pretreatment of the catalyst, 100Fe/3.6Si/0.71K at a relatively high pressure of 12 atms. in syngas did not give rise to the formation any carbide and FT activity was poor.

  3. Study of Fe-Co Nanocomposite Films

    SciTech Connect

    Lancok, A.; Klementova, M.; Kohout, J.; Miglierini, M.; Fendrych, F.; Lancok, J.

    2010-07-13

    Moessbauer study of nanogranular ferromagnetic FeCo films is presented. Two ways of production of nanocomposite systems were employed: (i) hollow cathode plasma jet deposition process, and (ii) laser ablation from Fe-Co metallic targets by means of a KrF excimer laser and r.f. magnetron sputtering. Complementary information on the composition of the samples were obtained by nuclear magnetic resonance of {sup 57}Fe and {sup 59}Co nuclei, conversion electron Moessbauer spectroscopy, and high resolution transmission electron microscopy. The films contain crystalline nanoparticles, 5-20 nm in size, embedded in an amorphous matrix.

  4. Iron-oxide Aerogel and Xerogel Catalyst Formulations: Characterization by 57Fe Mössbauer and XAFS Spectroscopies

    SciTech Connect

    Huggins, F.; Bali, S; Huffman, G; Eyring, E

    2010-01-01

    Iron in various iron-oxide aerogel and xerogel catalyst formulations ({ge}85% Fe{sub 2}O{sub 3}; {le}10% K, Co, Cu, or Pd) developed for possible use in Fischer-Tropsch synthesis (FTS) or the water-gas-shift (WGS) reaction has been examined by {sup 57}Fe Moessbauer spectroscopy. The seventeen samples consisted of both as-prepared and calcined aerogels and xerogels and their products after use as catalysts for FTS or the WGS reaction. Complementary XAFS spectra were obtained on the occurrence of the secondary elements in some of the same materials. A broad, slightly asymmetric, two-peak Moessbauer spectrum was obtained from the different as-prepared and calcined catalyst formulations in the majority of cases. Such spectra could only be satisfactorily fit with three quadrupole doublet components, but no systematic trends in the isomer shift and quadrupole splitting parameters and area ratios of the individual components could be discerned that reflected variations in the composition or preparation of the aerogel or xerogel materials. However, significant reductions were noted in the Moessbauer effective thickness (recoilless absorption effect per unit mass of iron) parameter, {chi}{sub eff}/g, determined at room temperature, for aerogels and xerogels compared to bulk iron oxides, reflecting the openness and lack of rigidity of the aerogel and xerogel structures. Moessbauer measurements for two aerogels over the range from 15 to 292 K confirmed the greatly diminished nature of this parameter at room temperature. Major increases in the effective thickness parameter were observed when the open structure of the aerogel or xerogel collapsed during calcination resulting in the formation of iron oxides (hematite, spinel ferrite). Similar structural changes were indicated by increases in this parameter after use of iron-oxide aerogels as catalysts for FTS or the WGS reaction, during which the iron-oxide aerogel was converted to a mixture of nonstoichiometric magnetite and

  5. Moessbauer spectroscopic study of phase conversions of an iron-containing oxide catalyst for oxidative dehydrogenation of butenes

    SciTech Connect

    Golub'ev, A.V.; Matveev, A.I.; Amirbekov, E.N.; Maksimov, Yu.V.; Suzdalev, I.P.

    1988-06-01

    Moessbauer spectroscopy was used to study the structure of ..gamma..-Al/sub 2/O/sub 3/-supported iron oxide, which is catalytically active in the oxidative dehydrogenation of butenes to divinyl. The phase conversions of the catalyst were investigated after treating it in reducing (butenes) and reaction (butenes + oxygen + water vapor) media and after regeneration in a stream of oxygen. It is shown that the supported phase changes from a structure similar to hematite (..cap alpha..-Fe/sub 2/O/sub 3/) to spinel structure both under the effect of butenes and the reaction mixture. When this happens ion exchange occurs between the spinel and the support, with the formation of partly hydrated complexes of Fe/sup 2 +/ ions in an asymmetric environment of O/sup 2 -/ ions and OH/sup -/ groups of the lattice of the support. These complexes vanish upon reoxidation of the catalyst, and part of the spinel is oxidized to hematite.

  6. Moessbauer and magnetic study of Mn, Zr and Cd substituted W-type hexaferrites prepared by co-precipitation

    SciTech Connect

    Iqbal, Muhammad Javed; Khan, Rafaqat Ali; Mizukami, Shigemi; Miyazaki, Terunobu

    2011-11-15

    Highlights: {yields} Zr and Cd ions substitute tetrahedral 4e and 4f{sub IV} sites while Mn ions occupy octahedral 6g and 4f sites. {yields} Doping of W-type hexaferrites with Mn, Zr and Cd improves the values of M{sub s} and M{sub r}. {yields} The enhancement of magnetic characteristic togetherwith the formation of rice shaped W-type hexaferrites nanoparticles is promising for imaging and sensing devices. {yields} The synthesized materials are suitable for magnetic data storage with high density. -- Abstract: BaCo{sub 2-x}Mn{sub x}Fe{sub 16-2y}(Zr-Cd){sub y}O{sub 27} (x = 0-0.5 and y = 0-1.0) hexaferrite nanocrystallites of average sizes in the range of 33-42 nm are synthesized by the chemical co-precipitation method. The synthesized materials are characterized using different techniques including X-ray diffraction (XRD), energy dispersive X-ray florescence (ED-XRF), scanning electron microscope (SEM), Moessbauer spectrometer and vibrating-sample magnetometer (VSM). Based on analysis of the data obtained from Moessbauer spectral studies, doping is believed to have occurred preferably in the vicinity of 12k sub-lattice, i.e. f{sub IV} (4e, 4f{sub IV}), 2b (6g, 4f) and 2d site. Variations in the saturation magnetization (77.1-60.9 emu g{sup -1}), remanent magnetization (22.08-31.23 emu g{sup -1}) and coercivity (1570.1-674.7 Oe) exhibit tunable behavior with dopant content and therefore can be useful for application in various magnetic devices.

  7. Magnetic properties of Al/57Fe/Cr multilayers

    NASA Astrophysics Data System (ADS)

    Jani, Snehal; Lakshmi, N.; Jain, Vishal; Reddy, V. R.; Gupta, Ajay; Venugopalan, K.

    2013-06-01

    Conversion Electron Mössbauer Spectroscopy (CEMS) and DC magnetization are used to compare magnetic properties of as-deposited multilayer (MLS) and Fe2CrAl thin film made from Al/57Fe/Cr MLS deposited by ion beam sputtering and then annealed in UHV. Interdiffusion of elements on annealing sample-1 at 500°C leads to formation of a single, disordered film of Fe2CrAl as evidenced by hyperfine field values obtained by CEMS in the film which compares well with that in bulk Fe2CrAl. CEMS also shows contributions from Fe, Fe/Cr and Fe/Al interfaces in the MLS. Saturation magnetization of as-deposited sample-1 is much less than pure Fe due to reduced Fe thickness because of interface formation and also reduction in Fe-Fe interaction due to intervening Al and Cr layers.

  8. High-Pressure-Hydrogen-Induced Spin Reconfiguration in GdFe2 Observed by 57Fe-Polarized Synchrotron Radiation Mössbauer Spectroscopy with Nuclear Bragg Monochromator

    NASA Astrophysics Data System (ADS)

    Mitsui, Takaya; Imai, Yasuhiko; Hirao, Naohisa; Matsuoka, Takahiro; Nakamura, Yumiko; Sakaki, Kouji; Enoki, Hirotoshi; Ishimatsu, Naoki; Masuda, Ryo; Seto, Makoto

    2016-12-01

    57Fe-polarized synchrotron radiation Mössbauer spectroscopy (PSRMS) with an X-ray phase plate and a nuclear Bragg monochromator was used to study ferrimagnetic GdFe2 in high-pressure hydrogen. The pressure-dependent spectra clearly showed a two-step magnetic transition of GdFe2. 57Fe-PSRMS with circular polarization gave direct evidence that the Fe moment was directed parallel to the net magnetization of the GdFe2 hydride at 20 GPa. This spin configuration was opposite to that of the initial GdFe2, suggesting an extreme weakening of the antiferromagnetic interaction between Fe and Gd. 57Fe-PSRMS enables the characterization of the nonuniform properties of iron-based polycrystalline powder alloys. The excellent applicability of 57Fe-PSRMS covers a wide range of scientific fields.

  9. In-field {sup 57}Fe Mössbauer spectroscopy below spin-flop transition in powdered troilite (FeS) mineral

    SciTech Connect

    Cuda, Jan Tucek, Jiri; Filip, Jan; Malina, Ondrej; Krizek, Michal; Zboril, Radek

    2014-10-27

    Powdered troilite (FeS), extracted from the Cape York IIIA octahedrite meteorite, was investigated employing in-field {sup 57}Fe Mössbauer spectroscopy. The study identified a typical behavior of polycrystalline antiferromagnetic material under external magnetic fields. The in-field evolution of the {sup 57}Fe Mössbauer spectra showed that the spin-flop transition in the FeS system occurs at a field higher than 5 T.

  10. Moessbauer study at room temperature of zinc ferrite as sorbent for hot coal gas desulphurization

    SciTech Connect

    Ahmed, M.A.

    2009-07-01

    Abstract: The method of using Moessbauer spectroscopy at room temperature was applied to assign the iron sites in one fresh zinc ferrite sample ZF with (1:1) concentration of their component oxides and calcined at 900C as well as its sulfurization derivatives at 750C in different coal gas of composition 0.5% H{sub 2}S + 0.5% H{sub 2}; 0.5% H{sub 2}S + 10% H{sub 2}; 0.5% H{sub 2}S + 25% H{sub 2}, and 0.5% H{sub 2}S + 10% H{sub 2}O (v). The most important iron phase obtained in the sulfurized samples, was pyrrhotite, Fe1-xS that exhibit three well different ional sextets. From the peak area and the associated magnetic hyperfine fields, the average magnetic field was calculated and indicates lowering in the number of iron vacancies whereas x is close to 0.

  11. Mark of the Moessbauer

    NASA Technical Reports Server (NTRS)

    2004-01-01

    This image, taken by an instrument called the microscopic imager on the Mars Exploration Rover Spirit, reveals an imprint left by another instrument, the Moessbauer spectrometer. The imprint is at a location within the rover wheel track named 'Middle of Road.' Both instruments are located on the rover's instrument deployment device, or 'arm.'

    Not only was the Moessbauer spectrometer able to gain important mineralogical information about this site, it also aided in the placement of the microscopic imager. On hard rocks, the microscopic imager uses its tiny metal sensor to determine proper placement for best possible focus. However, on the soft martian soil this guide would sink, prohibiting proper placement of the microscopic imager. After the Moessbauer spectrometer's much larger, donut-shaped plate touches the surface, Spirit can correctly calculate where to position the microscopic imager.

    Scientists find this image particularly interesting because of the compacted nature of the soil that was underneath the Moessbauer spectrometer plate. Also of interest are the embedded, round grains and the fractured appearance of the material disturbed within the hole. The material appears to be slightly cohesive. The field of view in this image, taken on Sol 43 (February 16, 2004), measures approximately 3 centimeters (1.2 inches) across.

  12. Moessbauer Effect Studies of Crystalline and Amorphous Iron-Based Alloys and of Corrosion Processes at Iron Surfaces.

    NASA Astrophysics Data System (ADS)

    Lin, Mou Ching

    In Part I of this thesis, Mossbauer effect spectroscopy has been used to measure the temperature dependence of the ('57)Fe effective magnetic hyperfine field, H(,eff), and isomer shift, (delta), across the entire Fe(,3)Al(,x)Si(,1 -x) system (0 (LESSTHEQ) x (LESSTHEQ) 1) from77K to the Curie temperature, the latter also being determined from these measurements. The observed dependence of H(,eff) and (delta) on Al concentration can be qualitatively understood in terms of the calculated band structure of Fe(,3)Si. ('57)Fe Mossbauer spectra have been obtained at both liquid nitrogen and room temperatures for a series of metallic glasses Fe(,82)B(,18-x)Be(,x) with 0 (LESSTHEQ) x (LESSTHEQ) 6 in Part II. The width of the probability distribution function of the effective magnetic hyperfine field remains approximately constant at a value of 80 kOe for all samples. However, the most probable value of the effective magnetic hyperfine field at liquid nitrogen temperature initially increases with Be content, but starts to decrease as x exceeds four. The isomer shift has a value of -0.032 mm/sec for samples with x (LESSTHEQ) 4 but changes to -0.050 mm/sec for samples with x > 4. The crystallization products obtained upon annealing the samples were identified. In the last part of this thesis, Mossbauer spectroscopy coupled with electrochemical measurements has been used to study in situ the effects of chloride ions on a passivated iron surface in boric acid-sodium borate buffer solution at a pH of 8.4. The Mossbauer spectrum of the oxide film formed after breakdown of the passive film by aggressive chloride ions consists of a doublet with line-width of 0.51 (+OR-) 0.03 mm/sec, isomer shift of 0.35 (+OR-) 0.02 mm/sec relative to the metallic iron, and quadrupole splitting of 0.79 (+OR-) 0.01 mm/sec. The quadrupole splitting differs from that of the passive film which has line-widths of 0.55 (+OR-) 0.08 mm/sec, an isomer shift of 0.36 (+OR-) 0.01 mm/sec, and a quadrupole

  13. Fe^2^+-Mg Order-Disorder Processes in Orthopyroxenes from São João Nepomuceno (IVA) Iron Meteorite: ^57Fe Mössbauer Spectroscopy and Single-Crystal X-Ray Diffraction Studies

    NASA Astrophysics Data System (ADS)

    Dos Santos, E.; Scorzelli, R. B.; Abdu, Y. A.; Varela, M. E.; Munayco, P.

    2013-09-01

    Here we study cation distribution in orthopyroxenes from São João Nepomuceno meteorite by Mössbauer spectroscopy, electron microprobe and single-crystal X-ray diffraction, in order to get insights into the thermal history of this meteorite.

  14. The 57Fe Synchrotron Mössbauer Source at the ESRF.

    PubMed

    Potapkin, Vasily; Chumakov, Aleksandr I; Smirnov, Gennadii V; Celse, Jean Philippe; Rüffer, Rudolf; McCammon, Catherine; Dubrovinsky, Leonid

    2012-07-01

    The design of a (57)Fe Synchrotron Mössbauer Source (SMS) for energy-domain Mössbauer spectroscopy using synchrotron radiation at the Nuclear Resonance beamline (ID18) at the European Synchrotron Radiation Facility is described. The SMS is based on a nuclear resonant monochromator employing pure nuclear reflections of an iron borate ((57)FeBO(3)) crystal. The source provides (57)Fe resonant radiation at 14.4 keV within a bandwidth of 15 neV which is tunable in energy over a range of about ±0.6 µeV. In contrast to radioactive sources, the beam of γ-radiation emitted by the SMS is almost fully resonant and fully polarized, has high brilliance and can be focused to a 10 µm × 5 µm spot size. Applications include, among others, the study of very small samples under extreme conditions, for example at ultrahigh pressure or combined high pressure and high temperature, and thin films under ultrahigh vacuum. The small cross section of the beam and its high intensity allow for rapid collection of Mössbauer data. For example, the measuring time of a spectrum for a sample in a diamond anvil cell at ∼100 GPa is around 10 min, whereas such an experiment with a radioactive point source would take more than one week and the data quality would be considerably less. The SMS is optimized for highest intensity and best energy resolution, which is achieved by collimation of the incident synchrotron radiation beam and thus illumination of the high-quality iron borate crystal within a narrow angular range around an optimal position of the rocking curve. The SMS is permanently located in an optics hutch and is operational immediately after moving it into the incident beam. The SMS is an in-line monochromator, i.e. the beam emitted by the SMS is directed almost exactly along the incident synchrotron radiation beam. Thus, the SMS can be easily utilized with all existing sample environments in the experimental hutches of the beamline. Owing to a very strong

  15. A Three-Pronged Attack To Investigate the Electronic Structure of a Family of Ferromagnetic Fe4Ln2 Cyclic Coordination Clusters: A Combined Magnetic Susceptibility, High-Field/High-Frequency Electron Paramagnetic Resonance, and (57)Fe Mössbauer Study.

    PubMed

    Schmidt, Sebastian F M; Koo, Changhyun; Mereacre, Valeriu; Park, Jaena; Heermann, Dieter W; Kataev, Vladislav; Anson, Christopher E; Prodius, Denis; Novitchi, Ghenadie; Klingeler, Rüdiger; Powell, Annie K

    2017-05-01

    We present the synthesis, structure, magnetic properties, as well as the Mössbauer and electron paramagnetic resonance studies of a ring-shaped [Fe(III)4Ln(III)2(Htea)4(μ-N3)4(N3)3(piv)3] (Ln = Y 1, Gd 2, Tb 3, Dy 4, Ho 5, Er, 6) coordination cluster. The Dy, Tb, and Ho analogues show blocking of the magnetization at low temperatures without applied fields. The anisotropy of the 3d ion and the exchange interaction between 3d and 4f ions in Fe4Ln2 complexes are unambiguously determined by high-field/high-frequency electron paramagnetic resonance measurements at low temperature. Ferromagnetic exchange interaction JFe-Ln is found which decreases upon variation of the Ln ions to larger atomic numbers. This dependence is similar to the behavior shown in the effective barrier values of complexes 3-5. Further information about the anisotropy of the Ln(3+) ions was gathered with (57)Fe Mössbauer spectroscopy, and the combination of these methods provides detailed information regarding the electronic structure of these complexes.

  16. Interface and temperature dependent magnetic properties of 57Fe/Ti/Co multilayers

    NASA Astrophysics Data System (ADS)

    Jain, Vishal; Lakshmi, N.; Sudheesh, V. D.; Jain, Vivek Kumar; Reddy, V. R.; Venugopalan, K.; Gupta, Ajay

    2014-09-01

    The effect of thermal annealing on the interface of 57Fe/Ti/Co multilayer and associated changes in microstructure, hyperfine field and bulk magnetic properties such as saturation magnetization, coercivity and squareness has been studied by X-ray diffraction, X-ray reflectivity, conversion electron Mössbauer spectroscopy and vibrating sample magnetometry. With increase in annealing temperature, interdiffusion leads to an increase in the roughness, hyperfine fields and coercivity along with a decrease in saturation magnetization. Annealing at 823 K leads to the formation of a FeCo phase along with the precipitation of Ti. The electrical resistivity (ρ) of the as-deposited sample decreases on annealing and hence the thermal coefficient of resistance (TCR) goes from negative to positive on annealing the samples. All samples show Curie temperature in excess of 723 K.

  17. 57Fe Mössbauer spectroscopy used to develop understanding of a diamond preservation index model

    NASA Astrophysics Data System (ADS)

    Yambissa, M. T.; Forder, S. D.; Bingham, P. A.

    2016-12-01

    57Fe Mössbauer spectroscopy has provided precise and accurate iron redox ratios Fe2+/Fe3+ in ilmenite, FeTiO3, found within kimberlite samples from the Catoca and Camatxia kimberlite pipes from N.E. Angola. Ilmenite is one of the key indicator minerals for diamond survival and it is also one of the iron-bearing minerals with iron naturally occurring in one or both of the oxidation states Fe3+ and Fe2+. For this reason it is a good indicator for studying oxygen fugacities ( fO2) in mineral samples, which can then be related to iron redox ratios, Fe2+/Fe3+. In this paper we demonstrate that the oxidation state of the ilmenite mineral inclusion from sampled kimberlite rock is a key indicator of the oxidation state of the host kimberlite assemblage, which in turn determines the genesis of diamond, grade variation and diamond quality. Ilmenite samples from the two different diamondiferous kimberlite localities (Catoca and Camatxia) in the Lucapa graben, N.E. Angola, were studied using Mössbauer spectroscopy and X-Ray Diffractometry, in order to infer the oxidation state of their source regions in the mantle, oxygen partial pressure and diamond preservation conditions. The iron redox ratios, obtained using Mössbauer spectroscopy, show that the Catoca diamond kimberlite is more oxidised than kimberlite found in the Camatxia pipe, which is associated within the same geological tectonic structure. Here we demonstrate that57Fe Mössbauer spectroscopy can assist geologists and mining engineers to effectively evaluate and determine whether kimberlite deposits are economically feasible for diamond mining.

  18. Gebel Kamil Iron Meteorite: 57Fe Mössbauer Spectroscopy and Magnetic Properties Data

    NASA Astrophysics Data System (ADS)

    Dos Santos, E.; Munayco, P.; Gattacceca, J.; Rochette, P.; Scorzelli, R. B.; Folco, L.

    2014-09-01

    In this work, we present magnetic properties data along with mineralogical characterization by 57Fe Mössbauer spectroscopy for a shrapnel of Gebel Kamil meteorite, in order to evaluate the thermal/shock history revealed by these techniques.

  19. Moessbauer spectroscopy studies of iron-catalysts used in Fischer-Tropsch (FT) processes. Quarterly technical progress report, January--March, 1994

    SciTech Connect

    Huffman, G.P.; Rao, K.R.P.M.

    1994-12-31

    The objective of this project is to carry out a Moessbauer spectroscopy study of Iron-based catalysts to identify iron phases present and correlate with water gas shift and FT activities. A total of 15 catalysts were evaluated so far. Results are presented on the amounts in each catalyst of the following phases: superparamagnetic phase, hematite ({alpha}-Fe{sub 2}O{sub 3}), magnetite (Fe{sub 3}O{sub 4}), Chi-carbide phase ({chi}-Fe{sub 5}C{sub 2}), and an epsilon-carbide phase ({var_epsilon}-Fe{sub 2.2}C).

  20. Moessbauer study on K/sub 2/Fe/sub 2/(CO)/sub 8/ in an external magnetic field

    SciTech Connect

    Arkhipov, I.L.; Kireev, N.V.; Stukan, R.A.; Yunusov, S.M.

    1988-03-01

    We consider in more detail what changes occur in the Moessbauer parameters when apical and equatorial CO groups are replaced by Fe(CO)/sub 4//sup =/ in the trigonal bipyramidal Fe(CO)/sub 5/ molecule. We use Bancroft's concept of the partial contributions to the quadrupole splitting (QS). The main difference between the HFS parameters for the Moessbauer spectra for the possible structures will be a marked difference in the asymmetry parameters. Here /eta/ can be determined for 1/2 /yields/ 3/2 transitions if there is combined hyperfine magnetic and quadrupole interaction. In a diamagnetic (K/sub 2/Fe/sub 2/(CO)/sub 8/), such combined interaction can occur only from the use of external magnetic fields. The Moessbauer spectra were recorded in an Oxford Instruments cryostat having a superconducting solenoid at 4.2 K without a field or with a longitudinal field of 4.6 T. The spectra show that the EFG tensor for K/sub 2/Fe/sub 2/(CO)/sub 8/ is axially symmetric (/eta/ 0) and that the sign of QS is positive.

  1. Moessbauer-Fresnel zone plate as nuclear monochromator

    SciTech Connect

    Mooney, T.M.; Alp, E.E.; Yun, W.B.

    1992-06-01

    Zone plates currently used in x-ray optics derive their focusing power from (a spatial variation of) the electronic refractive index -- that is, from the collective effect of electronic x-ray-scattering amplitudes. Nuclei also scatter x rays, and resonant nuclear-scattering amplitudes, particularly those associated with Moessbauer fluorescence, can dominate the refractive index for x-rays whose energies are very near the nuclear-resonance energy. A zone plate whose Fresnel zones are filled alternately with {sup 57}Fe and {sup 56}Fe ({sup 57}Fe has a nuclear resonance of natural width {Gamma} = 4.8 nano-eV at 14.413 keV; {sup 56}Fe has no such resonance) has a resonant focusing efficiency; it focuses only those x-rays whose energies are within several {Gamma} of resonance. When followed by an absorbing screen with a small pinhole, such a zone plate can function as a synchrotron-radiation monochromator with an energy resolution of a few parts in 10{sup 12}. The energy-dependent focusing efficiency and the resulting time-dependent response of a resonant zone plate are discussed.

  2. Surface analysis of mixed-conducting ferrite membranes by the conversion-electron Moessbauer spectroscopy

    SciTech Connect

    Waerenborgh, J.C.; Tsipis, E.V.; Yaremchenko, A.A.; Kharton, V.V.

    2011-09-15

    Conversion-electron Moessbauer spectroscopy analysis of iron surface states in the dense ceramic membranes made of {sup 57}Fe-enriched SrFe{sub 0.7}Al{sub 0.3}O{sub 3-{delta}} perovskite, shows no traces of reductive decomposition or carbide formation in the interfacial layers after operation under air/CH{sub 4} gradient at 1173 K, within the limits of experimental uncertainty. The predominant trivalent state of iron cations at the membrane permeate-side surface exposed to flowing dry methane provides evidence of the kinetic stabilization mechanism, which is only possible due to slow oxygen-exchange kinetics and enables long-term operation of the ferrite-based ceramic reactors for natural gas conversion. At the membrane feed-side surface exposed to air, the fractions of Fe{sup 4+} and Fe{sup 3+} are close to those in the powder equilibrated at atmospheric oxygen pressure, suggesting that the exchange limitations to oxygen transport are essentially localized at the partially reduced surface. - Graphical Abstract: Conversion-electron Moessbauer spectroscopy analysis of dense ceramic membranes made of {sup 57}Fe-enriched SrFe{sub 0.7}Al{sub 0.3}O{sub 3-{delta}} perovskite, shows no reductive decomposition in thin interfacial layers after testing under air/CH{sub 4} gradient, enabling stable operation of the ferrite-based ceramic reactors for partial oxidation of methane. Highlights: > Conversion-electron Moessbauer spectroscopy is used for mixed-conducting membranes. > No decomposition is detected in the membrane surface layers under air/CH{sub 4} gradient. > Due to kinetic stabilization, Fe{sup 3+} states prevail at the surface exposed to methane. > Transmission Moessbauer spectra show perovskite decomposition on equlibration in CH{sub 4}. > Ferrite-based ceramic reactors can stably operate under air/CH{sub 4} gradient.

  3. The 57Fe hyperfine interactions in human liver ferritin and its iron-polymaltose analogues: the heterogeneous iron core model

    NASA Astrophysics Data System (ADS)

    Oshtrakh, M. I.; Alenkina, I. V.; Semionkin, V. A.

    2016-12-01

    Human liver ferritin and its iron-polymaltose pharmaceutical analogues Ferrum Lek, Maltofer® and Ferrifol® were studied using Mössbauer spectroscopy at 295 and 90 K. The Mössbauer spectra were fitted on the basis of a new model of heterogeneous iron core structure using five quadrupole doublets. These components were related to the corresponding more or less close-packed iron core layers/regions demonstrating some variations in the 57Fe hyperfine parameters for the studied samples.

  4. Moessbauer spectroscopy study of the aging and tempering of high nitrogen quenched Fe-N alloys: Kinetics of formation of Fe{sub 16}N{sub 2} nitride by interstitial ordering in martensite

    SciTech Connect

    Fall, I.; Genin, J.M.R. |

    1996-08-01

    The distribution of nitrogen atoms in austenite and during the different stages of aging and tempering of martensite is studied by Moessbauer spectroscopy, X-ray diffraction, and transmission electron microscopy (TEM). Transmission Moessbauer spectroscopy (TMS) and conversion electron Moessbauer spectroscopy (CEMS) are used for studying the austenite phase where the distribution of nitrogen atoms is found to depend on the nitriding method, gas nitriding in the authors` case, or ion implantation. Conversion electron Moessbauer spectroscopy, which concerns a depth predominantly less than 200 nm, reveals a nitrogen atom distribution different from that found in the bulk by TMS. The identification and kinetics of the stages of aging and tempering of martensite are followed by TMS measurements, and the phase characterization is confirmed by X-ray diffraction and TEM. The major stages are the early ordering of nitrogen atoms, which leads to small coherent precipitates of {alpha}-Fe{sub 16}N{sub 2}; the passage by thickening to semicoherent precipitates of {alpha}-Fe{sub 16}N{sub 2}; the dissolution of {alpha}-Fe{sub 16}N{sub 2} with the concomitant formation of {gamma}-Fe{sub 4}N; and the decomposition of retained austenite by tempering. The three first stages correspond to activation energies of 95, 126, and 94 kJ/mole, respectively, consistent with the nitrogen diffusion for the first and third stages and the dislocation pipe diffusion of iron for the second.

  5. Moessbauer Studies of Exchange-Coupled Two-Iron Centers in Proteins

    NASA Astrophysics Data System (ADS)

    Sage, James Timothy

    This thesis reports Mossbauer measurements on three derivatives of the oxygen-transport protein hemerythrin and on the oxidized and reduced forms of uteroferrin, a purple acid phosphatase isolated from porcine uterine fluid. Both proteins contain an exchange-coupled pair of iron atoms coordinated directly to amino acid side chains. A model that takes account of both the exchange coupling and the zero-field splitting at each site is presented and used to describe the magnetic properties of the ground spin multiplet of a pair of coupled spins. One notable feature of the model is the fact that the g- and A-tensors of the coupled system may be quite anisotropic even if the corresponding single-site tensors are not. The model is applied in several Kramers systems and explains some unusual observations. In reduced uteroferrin, unexpectedly large anisotropies in the hyperfine tensor at the ferric site are rationalized naturally and in a way consistent with the other mag- netic properties. Similar observations on a sulfide derivative of hemerythrin appear to be susceptible to the same sort of expla- nation, although the Mossbauer simulations are not as refined. An unusual EPR spectrum observed in a nitric oxide derivative of deoxyhemerythrin is also explicable in the spin-coupling model; the corresponding Mossbauer spectra are reported but have not been analyzed in detail. Preliminary studies of some non-Kramers systems are also presented. The Mossbauer spectrum of an azide derivative of deoxyhemerythrin broadens in a small applied field, indicating the presence of a near degeneracy. The spectrum of oxidized utero- ferrin broadens as the temperature is raised, even in the absence of an applied field. No fully adequate explanation for the latter observation is apparent.

  6. Hydrometallurgical Extraction of Zinc and Copper A 57Fe-Mössbauer and XRD Approach

    NASA Astrophysics Data System (ADS)

    Mulaba-Bafubiandi, A. F.; Waanders, F. B.

    2005-02-01

    The most commonly used route in the hydrometallurgical extraction of zinc and copper from a sulphide ore is the concentrate roast leach electro winning process. In the present investigation a zinc copper ore from the Maranda mine, located in the Murchison Greenstone Belt, South Africa, containing sphalerite (ZnS) and chalcopyrite (CuFeS2), was studied. The 57Fe-Mössbauer spectrum of the concentrate yielded pyrite, chalcopyrite and clinochlore, consistent with XRD data. Optimal roasting conditions were found to be 900°C for 3 h and the calcine produced contained according to X-ray diffractometry equal amounts of franklinite (ZnFe2O4) and zinc oxide (ZnO) and half the amount of willemite (Zn2SiO4). The Mössbauer spectrum showed predominantly franklinite (59%), hematite (6%) and other Zn- or Cu-depleted ferrites (35%). The latter could not be detected by XRD analyses as peak overlapping with other species occurred. Leaching was done with HCl, H2SO4 and HNO3, to determine which process would result in maximum recovery of Zn and Cu. More than 80% of both were recovered by using either one of the three techniques. From the residue of the leaching, the Fe-compounds were precipitated and <1% of the Zn and Cu was not recovered.

  7. Probe Mössbauer spectroscopy of mechanical alloying in binary Cr‐{sup 57}Fe(1 at%) system

    SciTech Connect

    Elsukov, Evgeny P. Kolodkin, Denis A. Ul'yanov, Alexander L. Porsev, Vitaly E.

    2014-10-27

    Solid state reactions during mechanical alloying (MA) in a binary mixture of powdered Cr and {sup 57}Fe in atomic ratio of 99:1 have been studied using {sup 57}Fe Mössbauer spectroscopy, X-ray diffraction and Auger spectrometry. The proposed model of MA includes formation of Cr(Fe){sub x}O{sub y} oxides at the contact places of Cr and Fe particles, formation of nanostructure with simultaneous dissolution of the oxides, penetration of Fe atoms along grain boundaries in close-to-boundary distorted zones of interfaces in a substitutional position, formation of the substitutional solid solution of Fe in Cr in the body of grains. It was shown that the increase in the BCC lattice parameter on increasing the milling time is due to the dissolution of oxides and formation of interstitial solid solution of O in Cr. There were established substantial differences in consumption of BCC Fe in a Mg → Al → Si → Cr sequence due to the major role of chemical interaction of Mg(Al,Si,Cr) with Fe.

  8. Magnetic hyperfine field at diluted {sup 57}Fe in vapor-quenched heavy-rare-earth films

    SciTech Connect

    Passamani, E.C.; Baggio-Saitovitch, E.; Micklitz, H.

    1997-05-01

    In this work, we combine vapor-quenching technique at low temperature (20 K) and {ital in situ} {sup 57}Fe M{umlt o}ssbauer spectroscopy at different temperatures (7{endash}300 K) to study out-of-equilibrium solubility and magnetic properties of {sup 57}Fe(5at.{percent}) in some magnetic heavy-rare-earth (RE) metals (RE=Dy, Ho, Er, and Tm). The spectra were fitted using the full Hamiltonian including electric quadrupole and magnetic interactions. Two magnetic components are observed in the 7 K M{umlt o}ssbauer spectra: one with a magnetic hyperfine field (B{sub hf}) varying between 5.3(2) and 1.9(2) T, which has been attributed to Fe at a substitutional site, and the other one, with a smaller field ({lt}2.1T), which is assumed to be due to Fe at an interstitial site. The behavior of B{sub hf} for Fe at the substitutional site in the different RE metals scales with the de Gennes factor. {copyright} {ital 1997} {ital The American Physical Society}

  9. Inelastic scattering in condensed matter with high intensity Moessbauer radiation

    SciTech Connect

    Yelon, W.B.; Schupp, G.

    1993-02-01

    The QUEGS facility at MURR has produced a number of new results and demonstrated the range of potential applications of high resolution, high intensity Moessbauer scattering. This work has been carried out by both MU and Purdue researchers and includes published results on Na, W, pentadecane, polydimethylsiloxane and other systems, manuscripts submitted on alkali halides (Phys. Rev. B) and accurate Moessbauer lineshape measurements (Phys. Rev. C), and manuscripts in preparation on glycerol, NiAl and Moessbauer spectra obtained by modulating a scattering crystal. Recently, new collaborations have been initiated which will substantially enhance our efforts. These are with W. Steiner (Vienna), G. Coddens (Saclay), and R. D. Taylor (Los Alamos). Steiner is experienced with Fe-57 Moessbauer scattering, while Coddens specializes in quasielastic neutron scattering; both of these areas naturally complement our work. R. D. Taylor has pioneered Moessbauer spectroscopy from the time of its discovery and has already made important contributions to our study of lattice dynamics and superconductivity for lead alloyed with small quantities of tin. At the same time, a significant instrument upgrade is underway, funded in part by the DOE-URIP program.

  10. Mineralogy, 57Fe Mössbauer spectra and magnetization of chalcolithic pottery

    NASA Astrophysics Data System (ADS)

    Keller, R.; Masch, L.; Pohl, J.; Schmidbauer, E.

    2005-06-01

    Three chalcolithic pottery sherds, paint removed from the surface of each sherd, and an unheated red pigment (Tell-Halaf culture, Turkey) were analysed within the frame of archaeometric studies using mineralogical methods, 57Fe Mössbauer spectroscopy, magnetization and rotational hysteresis data. From mineralogical results, the individual minerals forming the cores of the sherds were determined. It was found that the sherds are lime-rich. High temperature X-ray analysis on comparable Ca-rich material showed that the established composition is consistent with a firing temperature of 750-950°C. Apart from the pigment, each Mössbauer spectrum of Fe-bearing components consists of dominating paramagnetic doublets, arising mostly from silicate phases, and of a six-line pattern with reduced intensity, due to ferri- and/or antiferromagnetic Fe-oxide phases. For three samples, an Fe3+ silicate component of the spectra is clearly dominating, which points to oxidizing conditions during firing. For the others Fe2+ and Fe3+ components occur in about equal intensities. For the pigment, the magnetic sextet is of similar intensity to the Fe3+ silicate component. From magnetic analysis of ferrimagnetic phases it follows that a low percentage of particles of solid solutions γ-Fe2O3 Fe3O4 exist, probably in part ≤0.1 μm in diameter. The ferrimagnetic particles of at least one paint are probably covered by a thin layer of hematite as found from rotational hysteresis data. An attempt is made to draw conclusions from the experimental results, regarding the firing conditions of the sherds and paints.

  11. 57Fe NMR study of the magnetoelectric hexaferrite Ba0.5Sr1.5Zn2Fe12O22 and Ba0.5Sr1.5Zn2(Fe0.92Al0.08)12O22

    NASA Astrophysics Data System (ADS)

    Kwon, Sangil; Yoon, Dong Young; Lee, Soonchil; Chai, Yi Sheng; Chun, Sae Hwan; Kim, Kee Hoon

    2013-08-01

    Magnetoelectric hexaferrite Ba0.5Sr1.5Zn2Fe12O22 (BSZFO) and Ba0.5Sr1.5Zn2(Fe0.92Al0.08)12O22 (BSZFAO) were investigated by 57Fe nuclear magnetic resonance (NMR). The spin-canting angles of all NMR peaks were measured to assign each peak to corresponding Fe3+ sites. It was revealed that the spin-canting angle of Fe3+ ions at off-centered octahedra is fixed and Al3+ ions substitute for Fe3+ ions at those sites. The temperature dependence of the NMR frequency indicates that the low-temperature excitation is spin wave in ferromagnetic phase.

  12. 57 Fe Mössbauer probe of spin crossover thin films on a bio-membrane

    NASA Astrophysics Data System (ADS)

    Naik, Anil D.; Garcia, Yann

    2012-03-01

    An illustrious complex [Fe(ptz)6](BF4)2 (ptz = 1-propyl-tetrazole) ( 1) which was produced in the form of submicron crystals and thin film on Allium cepa membrane was probed by 57Fe Mossbauer spectroscopy in order to follow its intrinsic spin crossover. In addition to a weak signal that corresponds to neat SCO compound significant amount of other iron compounds are found that could have morphed from 1 due to specific host-guest interaction on the lipid-bilayer of bio-membrane. Further complimentary information about biogenic role of membrane, was obtained from variable temperature Mossbauer spectroscopy on a ~5% enriched [57Fe(H2O)6](BF4)2 salt on this membrane.

  13. Novel superconducting characteristics and unusual normal-state properties in iron-based pnictide superconductors: 57FeNMR and 75AsNQR/NMR studies in REFeAsO 1- y (RE = La, Pr, Nd) and Ba 0.6K 0.4Fe 2As 2

    NASA Astrophysics Data System (ADS)

    Mukuda, H.; Terasaki, N.; Yashima, M.; Nishimura, H.; Kitaoka, Y.; Iyo, A.

    2009-05-01

    We discuss the novel superconducting characteristics and unusual normal-state properties of iron (Fe)-based pnictide superconductors REFeAsO 1- y (RE = La, Pr, Nd) and Ba 0.6K 0.4Fe 2As 2 ( Tc = 38 K) by means of 57FeNMR and 75AsNQR/NMR. In the superconducting state of LaFeAsO 0.7 ( Tc = 28 K), the spin component of the 57Fe-Knight shift decreases to almost zero at low temperatures, which provide firm evidence of the superconducting state formed by spin-singlet Cooper pairing. The nuclear spin-lattice relaxation rates (1/ T1) in LaFeAsO 0.7 and Ba 0.6K 0.4Fe 2As 2 exhibit a T3-like dependence without a coherence peak just below Tc, indicating that an unconventional superconducting state is commonly realized in these Fe-based pnictide compounds. All these events below Tc are consistently argued in terms of an extended s ±-wave pairing with a sign reversal of the order parameter among Fermi surfaces. In the normal state, 1/ T1T decreases remarkably upon cooling for both the Fe and As sites of LaFeAsO 0.7. In contrast, it gradually increases upon cooling in Ba 0.6K 0.4Fe 2As 2. Despite the similarity between the superconducting properties of these compounds, a crucial difference was observed in their normal-state properties depending on whether electrons or holes are doped into the FeAs layers. These results may provide some hint to address a possible mechanism of Fe-based pnictide superconductors.

  14. 57Fe Mössbauer investigations of manganese-containing spinels

    NASA Astrophysics Data System (ADS)

    Bluncson, C. R.; Thompson, G. K.; Evans, B. J.

    1994-12-01

    Cation distributions and related order-disorder phenomena in the naturally occurring Mn-spinels: iwakiite, galaxite and franklinite, have been investigated by means of57Fe Mössbauer spectroscopy. Previous measurements on an iwakiite sample indicated the existence of Mn-rich and Mn-poor regions. This interpretation has been confirmed in this investigation by further measurements on annealed iwakiite samples. The57Fe Mössbauer spectrum of galaxite from Bald Knob, NC, is a well-resolved quadrupole doublet and indicates the presence of a single crystallographic Fe3+ species. A “galaxite” sample from Thailand exhibited a complex spectrum of Fe2+ and Fe3+ quadrupole doublets: This sample has been misidentified and should be regarded as a member of the (Mg, Fe)(Al, Fe)2O4 series. The57Fe hyperfine parameters of a rare franklinite from Längban, Sweden, are very close to those for synthetic zinc ferrite, confirming electron microprobe results of an unusually high zinc content.

  15. Ordering and oxygen content effects in YBa sub 2 (Cu sub 1 minus x Fe sub x ) sub 3 O sub 7 samples observed by high-temperature Moessbauer spectroscopy

    SciTech Connect

    Saitovitch, E.B.; Scorzelli, R.B.; Azevedo, I.S.; dos Santos, C.A. )

    1990-05-01

    We report here {ital in} {ital situ} high-temperature {sup 57}Fe Moessbauer measurements on YBa{sub 2}(Cu{sub 1{minus}{ital x}}Fe{sub {ital x}}){sub 3}O{sub 7} samples in controlled oxygen atmosphere, in air, or in vacuum. In these conditions, fundamental information can be obtained related to the thermal stability of the different Fe species, as well as the mechanism of oxygen loss.

  16. Mössbauer investigations of hyperfine interactions features of {sup 57}Fe nuclei in BiFeO{sub 3} ferrite

    SciTech Connect

    Sobolev, Alexey Presniakov, Igor Rusakov, Vyacheslav Matsnev, Mikhail; Gorchakov, Dmitry; Glazkova, Iana; Belik, Alexey

    2014-10-27

    New results of {sup 57}Fe Mössbauer studies on BiFeO{sub 3} powder sample performed at various temperatures above and below magnetic phase transitions point T{sub N} ≈ 640K are reported. We have performed self-consistent calculations of the lattice contributions to the EFG tensor, taking into account dipole moments of the O{sup 2−} and Bi{sup 3+} ions. Low-temperature {sup 57}Fe Mössbauer spectra recorded at T < T{sub N} were analyzed assuming an anharmonic cycloidal modulation of the Fe{sup 3+} magnetic moments. The cycloidal modulation of the iron spin was described with the elliptic Jacobi function sn[(±4K(m)/λ)x,m]. The good fit of the experimental spectra was obtained for the anharmonicity m = 0.44 ± 0.04 (T = 4.9K) resulting from the easy-axis magnetic anisotropy.

  17. The Miniaturized Moessbauer Spectrometer MIMOS II for the Asteroid Redirect Mission(ARM): Quantative Iron Mineralogy And Oxidation States

    NASA Technical Reports Server (NTRS)

    Schroeder, C.; Klingelhoefer, G; Morris, R. V.; Yen, A. S.; Renz, F.; Graff, T. G.

    2016-01-01

    The miniaturized Moessbauer spectrometer MIMOS II is an off-the-shelf instrument with proven flight heritage. It has been successfully deployed during NASA’s Mars Exploration Rover (MER) mission and was on-board the UK-led Beagle 2 Mars lander and the Russian Phobos-Grunt sample return mission. A Moessbauer spectrometer has been suggested for ASTEX, a DLR Near-Earth Asteroid (NEA) mission study, and the potential payload to be hosted by the Asteroid Redirect Mission (ARM). Here we make the case for in situ asteroid characterization with Moessbauer spectroscopy on the ARM employing one of three available fully-qualified flight-spare Moessbauer instruments.

  18. Influence of Ordering Phenomena on the Thermomechanical Processing of High-Si Electrical Steel Studied by Moessbauer Spectroscopy

    SciTech Connect

    Ruiz, Daniel; Ros-Yanez, Tanya; Houbaert, Yvan; Vandenberghe, Robert E.

    2005-04-26

    Fe-Si alloys with Si-contents up to 14 at.%Si (7.6 wt.%Si ) were produced by conventional casting and hot/cold rolled with different conditions of temperatures, pass reductions and cooling rates. The obtained thickness of the final sheet was between 0.5 and 0.7 mm for Si-steel up to 10 at.%Si (5.5 wt.%). Moessbauer spectroscopy was used to characterize the order evolution with the Si-content and the thermomechanical processing of the material. A new fitting program was developed for this purpose due to the known complexity of the Fe-alloys spectra. Results show that there is never complete disorder, i.e. binomial distribution of the atoms, whatever the Si-concentration is. Moreover, a clear tendency towards D03 ordering is observed. The obtained long-range order parameters prove a patent increase of the D03 order above 7 at.%Si (3.6 wt.%) which can be associated to the observed brittleness beyond this Si-amount. Concerning the relationship between order and thermomechanical processing, no big effect was found for low Si-contents (up to 6 at.%Si), while for higher amounts two results are clearly observed: (i) the slower the cooling after the hot rolling is, the higher the order is and (ii) cold deformation removes order in a great way. This agrees with the need of fast cooling after hot rolling in order to increase the cold workability of the Si-steel.

  19. (Gamma scattering in condensed matter with high intensity Moessbauer radiation)

    SciTech Connect

    Not Available

    1992-01-01

    This report discusses: quasielastic scattering studies on glycerol; gamma-ray scattering from alkali halides; lattice dynamics in metals; Moessbauer neutron scattering, x-ray diffraction, and macroscopic studies of high {Tc} superconductors containing tungsten; NiAl scattering studies; and atomic interference factors and nuclear Casimir effect.

  20. Effect of 57Fe-goethite Amendment on Microbial Community Composition and Dynamics During the Transition from Iron to Sulfate Reduction

    NASA Astrophysics Data System (ADS)

    Moon, H.; McGuiness, L.; Kukkadapu, R. K.; Peacock, A.; Komlos, J.; Kerkhof, L.; Long, P. E.; Jaffe, P. R.

    2009-12-01

    Due to an increasing interest in microbial biostimulation for the purpose of U(VI) bioreduction, which proceeds via iron reduction, there is a growing need for a better understanding of the associated biogeochemical dynamics. This includes Fe(III) availability as well as the microbial community changes, including the activity of iron-reducers during the biostimulation period even after the onset of sulfate reduction. An up-flow column experiment was conducted with Old Rifle site sediments, where half of the columns had sediment that was augmented with 57Fe-goethite to track minute goethite changes after the onset of sulfate reduction, and to study the effects of increased Fe(III) levels on the overall biostimulation dynamics. The addition of the 57Fe-goethite did not delay the onset of sulfate reduction, but slightly suppressed the overall rate of sulfate reduction and hence acetate utilization. Mossbauer analyses confirmed that there was bioavailable iron present after the onset of sulfate reduction and that iron was still being reduced during sulfate reduction. Addition of the 57Fe-goethite to the sediment had a noticeable effect on the overall composition of the microbial population. 16S rRNA analyses of biostimulatd sediment using TRFLP showed that Geobacter sp. were still active and replicating after sulfate reduction had occurred for over 30 days. DNA fingerprints of the sediment-attached microbial communities were dominated by 5 TRFs, that comprised 25-57 % of the total profile. Augmentation of sediments with the 57Fe-goethite resulted in somewhat higher numbers of Geobacter-like species throughout the experiment, and during sulfate reduction slightly lower numbers of sulfate reducers. These columns also had a slightly improved U(VI) removal efficiency, which might be attributed to the higher Geobacter-like numbers.

  1. Visualization of 57Fe-Labeled Heme Isotopic Fine Structure and Localization of Regions of Erythroblast Maturation in Mouse Spleen by MALDI FTICR-MS Imaging

    NASA Astrophysics Data System (ADS)

    Kihara, Makoto; Matsuo-Tezuka, Yukari; Noguchi-Sasaki, Mariko; Yorozu, Keigo; Kurasawa, Mitsue; Shimonaka, Yasushi; Hirata, Michinori

    2017-08-01

    Epoetin beta pegol (continuous erythropoiesis receptor activator; C.E.R.A.), or methoxy-polyethylene glycol-modified epoetin beta, is a long-acting erythropoiesis stimulating agent (ESA) that effectively maintains hemoglobin levels. It promotes proliferation of erythroid progenitor cells in hematopoietic organs and leads to increased reticulocyte and hemoglobin levels. However, the detailed erythropoietic effects of various ESAs on their target organs have yet to be clarified, and new approaches are needed to analyze tissue iron localization with structural information. Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) techniques are widely used in basic pharmaceutical research. High-resolution Fourier transform ion cyclotron resonance (FTICR) mass spectrometry (MS) imaging enables the spatial mapping and identification of biomolecules. In this study, mice administered with C.E.R.A. were fed a diet containing the stable iron isotope 57Fe. The 57Fe-heme+ isotopic fine structure peak (m/z 617.1772) was separated from the non-labeled heme+ isotopic peak (Δ0.0029) by FTICR-MS with a resolving power of more than 500,000. We optimized the platform to analyze the distribution of 57Fe-heme in the spleen using MALDI FTICR-MS imaging. The combination of the ultrahigh resolution power of FTICR-MS and a stable isotope labeling technique has the potential to be very effective in basic pharmaceutical research. [Figure not available: see fulltext.

  2. Spin Fluctuations and Unconventional Superconductivity in the Fe-Based Oxypnictide Superconductor LaFeAsO0.7 Probed by 57Fe-NMR

    NASA Astrophysics Data System (ADS)

    Terasaki, Nobuyuki; Mukuda, Hidekazu; Yashima, Mitsuharu; Kitaoka, Yoshio; Miyazawa, Kiichi; Shirage, Parasharam M.; Kito, Hijiri; Eisaki, Hiroshi; Iyo, Akira

    2009-01-01

    We report 57Fe-NMR studies on the oxygen-deficient iron (Fe)-based oxypnictide superconductor LaFeAsO0.7 (Tc= 28 K) enriched by 57Fe isotope. In the superconducting state, the spin component of 57Fe-Knight shift decreases to almost zero at low temperatures, and the nuclear spin-lattice relaxation rate 57(1/T1) exhibits a T3-like dependence without the coherence peak just below Tc, which provide firm evidence of the unconventional superconducting state formed by spin-singlet Cooper pairing. All these events below Tc are consistently argued in terms of the extended s±-wave pairing with a sign reversal of the order parameter among Fermi surfaces. In the normal state, we found the remarkable decrease in 1/T1T upon cooling for both the Fe and As sites, which originates from the decrease in low-energy spectral weight of spin fluctuations over whole q space upon cooling below room temperature. Such behavior has never been observed for other strongly correlated superconductors where an antiferromagnetic interaction plays a vital role in mediating the Cooper pairing.

  3. A CEMS search for precipitate formation in 57Fe implanted ZnO

    NASA Astrophysics Data System (ADS)

    Bharuth-Ram, Krishanlal; Masenda, Hilary; Doyle, Terence B.; Geburt, Sebastian; Ronning, Carsten; Gunnlaugsson, Harald Palle

    2012-03-01

    Conversion electron Mössbauer Spectroscopy measurements have been made on ZnO single crystals implanted with 60 keV 57Fe to 4 and 8 at.% peak concentrations, and annealed up to 800°C. The spectra show quite strong changes with annealing, but no evidence of magnetic components, thus precluding the formation of large sized precipitates or secondary phases. Above an annealing temperature of 650°C, the dominant spectral component is a doublet with hyperfine parameters typical of Fe3 + , which is attributed to Fe3 + ions in nano-precipitates ˜5 nm in size.

  4. Microwave absorption and 57Fe Mössbauer properties of Ni-Ti doped barium hexaferrite

    NASA Astrophysics Data System (ADS)

    Harker, S. J.; Stewart, G. A.; Hutchison, W. D.; Amiet, A.; Tucker, D.

    2015-04-01

    The impact of doping the Fe component of barium hexaferrite with Ni0.5Ti0.5 is investigated using x-ray powder diffraction, 57Fe Mössbauer spectroscopy and microwave network analysis. The dopant ions exhibit a preference for the 2 b, 4 f 2 and 12 k-sites and the unit cell volume is observed to decrease. The ferromagnetic resonance frequency is reduced by about 11.5 GHz for each additional dopant ion per formula unit.

  5. Multilevel relaxation model for describing the Moessbauer spectra of nanoparticles in a magnetic field

    SciTech Connect

    Chuev, M. A.

    2012-04-15

    A theory is developed for the Moessbauer absorption spectra of an ensemble of single-domain particles in a magnetic field. This theory is based on the generalization of a relaxation model with a quantummechanical description of the stationary states of a particle and on the formalism of Liouville operators for describing the hyperfine interaction for a hyperfine field changing in both the magnitude and direction for various stationary states. The general scheme of calculating relaxation Moessbauer spectra in terms of a standard stochastic approach is substantially optimized using operations with block matrices and a unique tridiagonalization of high-rank non-Hermitian matrices with a simple nonorthogonal transformation in the calculation procedure. The resulting model can easily be implemented on a personal computer. It considers the physical mechanisms of formation of a hyperfine structure in a spectrum of nanoparticles in a real situation and self-consistently describes the qualitative features of the nontrivial evolution of spectra with the temperature and the magnetic-field direction and strength, which has been detected in {sup 57}Fe nucleus experiments performed on magnetic nanoparticles for half a century.

  6. 57Fe Mössbauer spectroscopy on disordered crystalline media with Ca-gallogermanate type structure. I. In the paramagnetic range

    NASA Astrophysics Data System (ADS)

    Barb, D.; Constantinescu, S.; Tarina, D.

    1995-12-01

    Polycrystalline strontium iron germanates of the type Sr3- y Ln y Fe2+ y Ge4- y O14(Ln=La, Nd; y=0, 1) were investigated by57Fe Mössbauer spectroscopy in the temperature range 4.2 300 K. The crystal chemistry and the distribution of Fe3+ ions in the structure, as well as the crystallographic inequivalence of the oxygen polyhedra occupied by iron, were studied over the whole paramagnetic temperature region. A correlation of the experimental data with a local environment computation is given.

  7. Application of 57Fe Mössbauer spectroscopy as a tool for mining exploration of bornite (Cu5FeS4) copper ore

    NASA Astrophysics Data System (ADS)

    Gainov, R. R.; Vagizov, F. G.; Golovanevskiy, V. A.; Ksenofontov, V. A.; Klingelhöfer, G.; Klekovkina, V. V.; Shumilova, T. G.; Pen'kov, I. N.

    2014-04-01

    Nuclear resonance methods, including Mössbauer spectroscopy,are considered as unique techniques suitable for remote on-line mineralogical analysis. The employment of these methods provides potentially significant commercial benefits for mining industry. As applied to copper sulfide ores, Mössbauer spectroscopy method is suitable for the analysis noted. Bornite (formally Cu5FeS4) is a significant part of copper ore and identification of its properties is important for economic exploitation of commercial copper ore deposits. A series of natural bornite samples was studied by 57Fe Mössbauer spectroscopy. Two aspects were considered: reexamination of 57Fe Mössbauer properties of natural bornite samples and their stability irrespective of origin and potential use of miniaturized Mössbauer spectrometers MIMOS II for in-situ bornite identification. The results obtained show a number of potential benefits of introducing the available portative Mössbauer equipment into the mining industry for express mineralogical analysis. In addition, results of some preliminary 63,65Cu nuclear quadrupole resonance (NQR) studies of bornite are reported and their merits with Mössbauer techniques for bornite detection discussed.

  8. Noncollinear Fe spin structure in (Sm-Co)/Fe exchange-spring bilayers: layer-resolved {sup 57}Fe Mssbauer spectroscopy and electronic structure calculations.

    SciTech Connect

    Uzdin, V. M.; Vega, A.; Khrenov, A.; Keune, W.; Kuncser, V. E.; Jiang, J. S.; Bader, S. D.

    2012-01-01

    Magnetization reversal in nanoscale (Sm-Co)/Fe (hard/soft) bilayer exchange-spring magnets with in-plane uniaxial magnetic anisotropy was investigated by magnetometry, conversion-electron Moessbauer spectroscopy (CEMS) and atomistic Fe spin-structure calculations. Magnetization loops along the easy direction exhibit signatures typical of exchange-spring magnets. In-field CEMS at inclined {gamma}-ray incidence onto thin (2 nm) {sup 57}Fe probe layers embedded at various depths in the 20-nm-thick natural (soft) Fe layer provides depth-dependent information (via the line-intensity ratio R{sub 23} as a function of the applied field H) about the in-plane rotation of Fe spins. A minimum in the R{sub 23}-vs-H dependence at (H{sub min}, R{sub min}) determines the field where Fe magnetic moments roughly adopt an average perpendicular orientation during their reversal from positive to negative easy-axis orientation. A monotonic decrease of H{sub min} with distance from the hard/soft interface is observed. Rotation of Fe spins takes place even in the interface region in applied fields far below the field of irreversible switching, H{sub irr}, of the hard phase. Formation of an Fe-Co alloy is detected in the interface region. For comparison, the noncollinear Fe spin structure during reversal and the resulting R{sub 23} ratio were obtained by electronic-structure calculations based on a quantum-mechanical Hamiltonian for itinerant electrons. The coupling at the hard/soft interface is described by the uniaxial exchange-anisotropy field, hint, as a parameter. Our calculated R{sub 23} ratios as a function of the (reduced) applied field h exhibit similar features as observed in the experiment, in particular a minimum at (h{sub min}, R{sub min}). R{sub min} is found to increase with hint, thus providing a measure of the interface coupling. Evidence is provided for the existence of fluctuations of the interface coupling. The calculations also show that the Fe spin spiral formed

  9. Moessbauer and magnetic studies of the ternary compound FeIn{sub 2}Se{sub 4}

    SciTech Connect

    Bodnar, I. V. Pauliukavets, S. A.; Trukhanov, S. V.; Fedotova, Yu. A.

    2012-05-15

    Single crystals of the ternary compound FeIn{sub 2}Se{sub 4} are grown by directional crystallization of the melt. The composition and structure of the single crystals are determined. The local states of iron ions in this compound are studied by nuclear {gamma}-resonance spectroscopy in transmission configuration. The temperature and field dependences of a specific magnetic moment for the ternary compound FeIn{sub 2}Se{sub 4} are measured in the temperature range 4-310 K in magnetic fields of 0-140 kOe. The reasons and mechanisms for magnetic state formation in single crystals of the obtained compound are discussed.

  10. a Moessbauer Effect and Fenske-Hall Molecular Orbital Study of the Electronic Properties of Organoiron Clusters.

    NASA Astrophysics Data System (ADS)

    Buhl, Margaret Linn

    The electronic properties of trinuclear iron, tetranuclear iron butterfly, iron-cobalt, and iron-copper clusters have been studied experimentally at 78K by the Mossbauer effect and theoretically by Fenske-Hall molecular orbital calculations. The Mossbauer effect isomer shift is very sensitive to the differences in the iron s-electron densities in these clusters and, as expected, decreases as the sum of the iron 4s Mulliken population and the Clementi and Raimondi effective nuclear charge increases. The molecular orbital wave functions and the Mulliken atomic charges are used to calculate the electric field gradient at the metal nuclei and the iron Mossbauer effect quadrupole splittings. The valence contribution was found to be the major component of the electric field gradient in all the clusters studied. In general the calculated value of Delta E_ {Q} is larger than the observed value, as a result of neglect of the valence Sternheimer factor, R. The metal charge depends upon its electronegativity and upon the nature of its Lewis base ligands. The carbonyl ligand carbon charge becomes more positive as the metal electronegativity increases. The oxygen charge becomes more negative as the anionic cluster charge increases, and in so doing, yields the maximum anionic charge separation. The electronic properties of the terminal carbonyl ligands are similar to those of carbon monoxide, whereas the electronic properties of the bridging carbonyl ligands are similar to those of the carbonyl group found in aldehydes and ketones.

  11. Moessbauer studies in zinc-manganese ferrites for use in measuring small velocities and accelerations with great precision

    NASA Technical Reports Server (NTRS)

    Escue, W. T.; Gupta, R. G.; Mendiratta, R. G.

    1975-01-01

    Mossbauer spectroscopy was used for a systematic study of the magnetic behavior of manganese and zinc in mixed ferrites. It was observed that Zn2+ has preference to substitute Mn2+ at interstitial sites where the metal ions are tetrahedrally coordinated with four oxygen neighbors. The internal magnetic hyperfine field at the tetrahedral iron site is larger than that at the octahedral site. The relaxation effects were observed to play an important role as the zinc contents were increased, while the spin-correlation time and the magnetic field were observed to decrease in strength. It is concluded that Mossbauer effect data on complex materials, when used in conjunction with other data, can provide useful insight into the origin of the microscopic properties of magnetic materials.

  12. Moessbauer Effect Study of Bi2O3. Na2O. B2O3. Fe2O3 Glass System

    SciTech Connect

    Salah, S.H.; Kashif, I.; Salem, S.M.; Mostafa, A.G.; El-Manakhly, K.A.

    2005-04-26

    Sodium-tetra-borate host glass containing both bismuth and iron cations were prepared obeying the composition (Na2B4O7)0.75 (Fe2O3)0.25-x (Bi2O3)x [where x = 0.0, 0.05, 0.10, 0.15, 0.20, and 0.25 mol.%]. X-ray diffraction indicated that all samples were in a homogeneous glassy phase. Moessbauer effect results showed that all iron ions appeared as Fe3+ ions occupying tetrahedral coordination state. The covalency of the Fe-O bond increased as bismuth oxide was gradually increased. IR measurements indicated the presence of some non-bridging oxygens and confirmed that iron ions occupy the tetrahedral coordination state. It was found also that, as Bi2O3 was gradually increased both magnetic susceptibility and specific volume decreased, while both density and molar volume increased.

  13. Nano-structure analysis of Fe implanted SnO2 films by 57Fe and 119Sn CEMS

    NASA Astrophysics Data System (ADS)

    Nomura, Kiyoshi; Reuther, Helfried

    2009-06-01

    SnO2 films were implanted with 57Fe at substrate temperatures of room temperature and 300°C. The chemical states of Fe and Sn were characterized by 57Fe CEMS and 119Sn CEMS, respectively. The implanted Fe species exist as Fe(II) and Fe(III) in SnO2 films, which also are reduced into Sn(II)on the implanted surface. The as prepared and post annealed at 500°C samples did not show Kerr effect, but the sample implanted with 1 × 1017 Fe ions/cm2 at 300°C showed Kerr effect although magnetic sextets were not clearly observed in the 57Fe CEM spectra. The Kerr effect disappeared after annealing. It suggests that the number of magnetic defects decreases by absorption of oxygen. Magnetic relaxation appeared in the case of low implantation of 5 × 1016 Fe ions/cm2, which is considered to be due to anti-ferromagnetism or paramagnetic relaxation.

  14. Moessbauer Analysis of Low-Temperature Bainite

    SciTech Connect

    Bruna, P.; Crespo, D.; Garcia-Mateo, C.; Bhadeshia, H.K.D.H.

    2005-04-26

    Low-temperature bainite, obtained by the transformation of austenite at temperatures as low as 200 deg. C for times as large as several days, has been reported to have extraordinary mechanical properties including the highest reported hardness of any bainitic steel. The unusual properties are a consequence of the fine scale of the microstructure, which contains bainite plates with thickness in the range 20-40 nm. The microstructure also contains carbon-enriched retained austenite which contributes to the properties via a number of mechanisms. In this work, the microstructure of a high carbon bainitic steel with Si to avoid cementite precipitation and Co to accelerate the transformation has been studied using Moessbauer spectroscopy for a series of samples transformed isothermally at 200 deg. C for time periods of 26, 34 and 96 hours. The total austenite content is almost identical ({approx}13 wt%) for these samples although the carbon concentrations of the phases differ as a function of transformation time. The austenite increases its carbon content from 5.4 atomic % after 26 h transformation to 6.3 at.% after 96 h, while the final bainitic phase retains about 2.2 at.% of C. These results are consistent with data obtained using atom probe tomography for samples transformed isothermally for 12 days.

  15. Observation of Enhancement of the Morin Transition Temperature in Iridium-Doped α-Fe2O3 Thin Film by 57Fe-Grazing Incidence Synchrotron Radiation Mössbauer Spectroscopy

    NASA Astrophysics Data System (ADS)

    Mitsui, Takaya; Mibu, Ko; Seto, Makoto; Kurokuzu, Masayuki; Pati, Satya Prakash; Nozaki, Tomohiro; Sahashi, Masashi

    2016-06-01

    The Morin transition of a (0001)-oriented iridium-doped α-Fe2O3 thin film deposited on an Al2O3(0001) substrate was studied by 57Fe-grazing incidence synchrotron radiation Mössbauer spectroscopy (GISRMS). Temperature-dependent spectra proved that the iridium doping markedly enhanced the Morin temperature of the α-Fe2O3 thin film; the iron spin directions were perpendicular to the film plane at temperatures below 100 °C, while they were in-plane at temperatures above 150 °C. The antiferromagnetic ordering was maintained far above 400 °C. The results demonstrated the availabilities of 57Fe-GISRMS, which enables a very quick evaluation of the magnetism in antiferromagnetic ultrathin films at high temperatures.

  16. Electronic state of 57Fe used as Mössbauer probe in the perovskites LaMO 3 ( M=Ni and Cu)

    NASA Astrophysics Data System (ADS)

    Presniakov, Igor; Demazeau, Gérard; Baranov, Alexei; Sobolev, Alexei; Gubaidulina, Tatyana; Rusakov, Viyacheslav

    2007-11-01

    For the first time a comparative study of rhombohedral LaNiO 3 and LaCuO 3 oxides, using 57Fe Mössbauer probe spectroscopy (1% atomic rate), has been carried out. In spite of the fact that both oxides are characterized by similar crystal structure and metallic properties, the behavior of 57Fe probe atoms in such lattices appears essentially different. In the case of LaNi 0.99Fe 0.01O 3, the observed isomer shift ( δ) value corresponds to Fe 3+ (3 d5) cations in high-spin state located in an oxygen octahedral surrounding. In contrast, for the LaCu 0.99Fe 0.01O 3, the obtained δ value is comparable to that characterizing the formally tetravalent high-spin Fe 4+(3 d4) cations in octahedral coordination within Fe(IV) perovskite-like ferrates. To explain such a difference, an approach based on the qualitative energy diagrams analysis and the calculations within the cluster configuration interaction method have been developed. It was shown that in the case of LaNi 0.99Fe 0.01O 3, electronic state of nickel is dominated by the d7 configuration corresponding to the formal ionic "Ni 3+-O 2-" state. On the other hand, in the case of LaCu 0.99Fe 0.01O 3 a large amount of charge is transferred via Cu-O bonds from the O:2 p bands to the Cu:3 d orbitals and the ground state is dominated by the d9L configuration ("Cu 2+-O" state). The dominant d 9L ground state for the (CuO 6) sublattice induces in the environment of the 57Fe probe cations a charge transfer Fe 3++O -( L)→Fe 4++O 2-, which transforms "Fe 3+" into "Fe 4+" state. The analysis of the isomer shift value for the formally "Fe 4+" ions in perovskite-like oxides clearly proved a drastic influence of the 4 s iron orbitals population on the Fe-O bonds character.

  17. Micromagnetic and Moessbauer spectroscopic investigation of strain-induced martensite in austenitic stainless steel

    SciTech Connect

    Meszaros, I.; Kaldor, M.; Hidasi, B.; Vertes, A.; Czako-Nagy, I.

    1996-08-01

    Strain-induced martensite in 18/8 austenitic stainless steel was studied. Magnetic measurements and Moessbauer spectroscopic investigations were performed to characterize the amount of {alpha}{prime}-martensite due to room-temperature plastic tensile loading. The effects of cold work and annealing heat treatment were explored using magnetic Barkhausen noise, saturation polarization, coercive force, hardness, and conversion electron Moessbauer spectroscopy. The suggested Barkhausen noise measurement technique proved to be a useful quantitative and nondestructive method for determining the ferromagnetic phase ratio of the studied alloy.

  18. Exogenous iron redistribution between brain and spleen after the administration of the 57Fe3O4 ferrofluid into the ventricle of the brain

    NASA Astrophysics Data System (ADS)

    Gabbasov, Raul; Polikarpov, Dmitry; Cherepanov, Valery; Chuev, Michael; Mischenko, Ilya; Loginiva, Nadezhda; Loseva, Elena; Nikitin, Maxim; Panchenko, Vladislav

    2017-04-01

    Iron clearance pathways after the injection of 57Fe3O4-based dextran-stabilized ferrofluid into the brain ventricles were studied by Mössbauer spectroscopy and histologically. The nanoparticles appeared in spleen tissues within 3 h after transcranial injection. We separated and independently estimated concentrations of iron encapsulated in nanoparticles and iron encapsulated in proteins in the all rat organs. It was found that the dextran coated initial nanoparticles of the ferrofluid disintegrated in the brain into separate superparamagnetic nanoparticles within a week after the injection.The nanoparticles completely exited from the brain in a few weeks. The exogenous iron appeared in the spleen in 3 h after the injection and remained in the spleen for more than month. The appearance of additional component in Mössbauer spectra of spleen samples revealed a fundamental difference in the mechanisms of processing of iron nanoparticles in this organ, which was also confirmed by histological examination.

  19. Gamma-resonance study of nanopowders with different dispersion and quasicrystalline phases in the Al-Cu-Fe system

    SciTech Connect

    Frolov, K. V. Mikheeva, M. N.; Lyubutin, I. S.; Nikonov, A. A.; Teplov, A. A.; Shaitura, D. S.; Abuzin, Yu. A.

    2007-11-15

    {sup 57}Fe Moessbauer spectroscopy has been used to monitor synthesis of quasicrystals in the Al-Cu-Fe system and study the influence of the size of quasicrystalline particles in powder samples of the Al{sub 63.1}Cu{sub 25.6}Fe{sub 11.3} alloy on the properties of synthesized materials. Quasicrystalline samples of different dispersion with particle sizes from 0.3 to 15 {mu}m have been studied in the temperature range 80-295 K. It is established that iron atoms in an Al{sub 63.1}Cu{sub 25.6}Fe{sub 11.3} quasicrystals occupy four types of structural positions, which differ in the atomic composition of the nearest environment. The results of the analysis suggest the dependence of the hyperfine-interaction parameters on the degree of sample dispersion. The components corresponding to iron atoms in both the surface layer and bulk of microparticles are isolated in the Moessbauer spectra. No magnetic hyperfine splitting has been found in the Moessbauer spectra in the entire temperature range. This fact suggests that a localized magnetic moment is absent in iron atoms.

  20. Analysis of Moessbauer Data from Mars: A Database and Artificial Neural Network for Identification of Iron-bearing Phases

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; deSouza, P. A.; Morris, R. V.; Klingelhoefer, G.

    2003-01-01

    The exploration of the planet Mars is one of the major goals within the Solar system exploration programs of the US-American space agency NASA and the European Space Agency ESA. In particular the search for water and life and understanding of the history of the surface and atmosphere will be the major tasks of the upcoming space missions to Mars. The miniaturized Moessbauer spectrometer MIMOS II has been selected for the NASA Mars-Exploration-Rover twin-mission to Mars in 2003 and the ESA 2003 Mars-Express Beagle 2 mission. Reduced in size and weight, in comparison to ordinary laboratory setup, the sensor head just weights approximately 400 g, with a volume of (50x50x90) cu mm, and holds two gamma-ray sources: the stronger for experiments and the weaker for calibrations. The collimator (in sample direction) also shields the primary radiation off the detectors. Around the drive four detectors are mounted. The detectors are made of Si-PIN-photodiodes in chip form (100 sq mm, thickness of 0.5 mm). The control unit is located in a separate electronics board. This board is responsible for the power supply, generation of the drive's velocity reference signal, read of the detector pulses to record the spectrum, data storage and communication with the host computer. After more than four decades from the discovery of the Moessbauer effect, more than 400 minerals were studied at different temperatures. Their Moessbauer parameters were reported in the literature, and have been recently collected in a data bank. Previous Mars-missions, namely Viking and Mars Pathfinder, revealed Si, Al, Fe, Mg, Ca, K, Ti, S and Cl to be the major constituents in soil and rock elemental composition of the red planet. More than 200 minerals already studied by Moessbauer spectroscopy contain significant amounts of these elements. A considerable number of Moessbauer studies were also carried out on meteorites and on Moon samples. Looking backward in the studies of the whole Moessbauer community

  1. Analysis of Moessbauer Data from Mars: A Database and Artificial Neural Network for Identification of Iron-bearing Phases

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; deSouza, P. A.; Morris, R. V.; Klingelhoefer, G.

    2003-01-01

    The exploration of the planet Mars is one of the major goals within the Solar system exploration programs of the US-American space agency NASA and the European Space Agency ESA. In particular the search for water and life and understanding of the history of the surface and atmosphere will be the major tasks of the upcoming space missions to Mars. The miniaturized Moessbauer spectrometer MIMOS II has been selected for the NASA Mars-Exploration-Rover twin-mission to Mars in 2003 and the ESA 2003 Mars-Express Beagle 2 mission. Reduced in size and weight, in comparison to ordinary laboratory setup, the sensor head just weights approximately 400 g, with a volume of (50x50x90) cu mm, and holds two gamma-ray sources: the stronger for experiments and the weaker for calibrations. The collimator (in sample direction) also shields the primary radiation off the detectors. Around the drive four detectors are mounted. The detectors are made of Si-PIN-photodiodes in chip form (100 sq mm, thickness of 0.5 mm). The control unit is located in a separate electronics board. This board is responsible for the power supply, generation of the drive's velocity reference signal, read of the detector pulses to record the spectrum, data storage and communication with the host computer. After more than four decades from the discovery of the Moessbauer effect, more than 400 minerals were studied at different temperatures. Their Moessbauer parameters were reported in the literature, and have been recently collected in a data bank. Previous Mars-missions, namely Viking and Mars Pathfinder, revealed Si, Al, Fe, Mg, Ca, K, Ti, S and Cl to be the major constituents in soil and rock elemental composition of the red planet. More than 200 minerals already studied by Moessbauer spectroscopy contain significant amounts of these elements. A considerable number of Moessbauer studies were also carried out on meteorites and on Moon samples. Looking backward in the studies of the whole Moessbauer community

  2. 57Fe NGR studies on three-stage hydroliquefaction of coals

    NASA Astrophysics Data System (ADS)

    Jamond, M.; Bacaud, R.; Bussiere, P.; Charcosset, H.; Nickel-Pepin-Donat, B.

    1990-06-01

    Iron Mössbauer spectroscopy has been performed on liquefaction residues of two different French coals. In a three-stage liquefaction of high volatile bituminous coal (Freyming), without an added catalyst, the coal pyrite is not entirely converted into pyrrhotites, whereas in the presence of an added catalyst, coal pyrite is totally transformed into more dispersed pyrrhotites than those from the sample without an added catalyst; furthermore, the whole added catalyst precursor is reduced into pyrrhotites. In the case of liquefaction of subbituminous coal (Gardanne), full conversion of coal pyrite into pyrrhotites (even without an added catalyst) occurs. In addition, in the presence of the added catalyst, besides pyrrhotites, FeS is evidenced. When molybdenum-iron oxide is added as a catalyst precursor, no mixed Fe-Mo phase is detected.

  3. Corrosion studies of iron and its alloys by means of57Fe Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Marco, J. F.; Dávalos, J.; Gracia, M.; Gancedo, J. R.

    1994-12-01

    Some of the advantages and limitations of Mössbauer spectroscopy when used in corrosion research are shown by using three examples taken from the work of the authors on (i) the passive layer of iron, (ii) the corrosion of weathering steels by SO2-polluted atmospheres and (iii) the performance of rust converters.

  4. Theory of Moessbauer line broadening due to diffusion

    SciTech Connect

    Schroeder, K.; Wolf, D.; Dederichs, P.H.

    1981-12-01

    We have calculated the line broadening of the Moessbauer line due to diffusion of Moessbauer atoms via single vacanices. We take into account the perturbation of vacancy jumps in the neighbourhood of an impurity Moessbauer atom (e.g. Fe in Al) using the 5-frequency model. The anisotropy of the line width is given by the Fourier transform of the final distribution of a Moessbauer atom after an encounter with a vacancy. This distribution is calculated by Monte Carlo computer simulation. 3 figures, 1 tables.

  5. Large low-energy M1 strength for ^{56,57}Fe within the nuclear shell model.

    PubMed

    Brown, B Alex; Larsen, A C

    2014-12-19

    A strong enhancement at low γ-ray energies has recently been discovered in the γ-ray strength function of ^{56,57}Fe. In this work, we have for the first time obtained theoretical γ decay spectra for states up to ≈8  MeV in excitation for ^{56,57}Fe. We find large B(M1) values for low γ-ray energies that provide an explanation for the experimental observations. The role of mixed E2 transitions for the low-energy enhancement is addressed theoretically for the first time, and it is found that they contribute a rather small fraction. Our calculations clearly show that the high-ℓ(=f) diagonal terms are most important for the strong low-energy M1 transitions. As such types of 0ℏω transitions are expected for all nuclei, our results indicate that a low-energy M1 enhancement should be present throughout the nuclear chart. This could have far-reaching consequences for our understanding of the M1 strength function at high excitation energies, with profound implications for astrophysical reaction rates.

  6. Spectroscopic characterization of 57Fe-reconstituted rubrerythrin, a non-heme iron protein with structural analogies to ribonucleotide reductase.

    PubMed

    Ravi, N; Prickril, B C; Kurtz, D M; Huynh, B H

    1993-08-24

    Rubrerythrin, a contraction of rubredoxin and hemerythrin, is the trivial name given to a non-heme iron protein isolated from Desulfovibrio vulgaris (Hildenborough). This protein, whose physiological function is unknown, was first characterized by J. LeGall et al. [(1988) Biochemistry 28, 1636] as being a homodimer of subunit M(r) = 21,900 with four Fe per homodimer distributed as two rubredoxin-type FeS4 centers and one hemerythrin-type diiron cluster. Subsequent analysis of the amino acid sequence of the rubrerythrin gene [Kurtz, D. M., Jr., & Prickril, B.C. (1991) Biochem. Biophys. Res. Commun. 181, 137] revealed an internal homology which suggested that each subunit can accommodate one diiron cluster. Here, we report a procedure for reconstitution of the as-isolated D. vulgaris rubrerythrin with 57Fe. The reconstituted protein was characterized by optical, electron paramagnetic resonance, and Mössbauer spectroscopies. The results indicate successful incorporation of 57Fe into the two types of sites and strongly suggest that each subunit of rubrerythrin can indeed accommodate one diiron cluster as well as one rubredoxin-type center. Combined with amino acid sequence analysis, the spectroscopic characterization further suggests that the rubrerythrin subunit contains a diiron site whose structure is more closely related to that in ribonucleotide reductase than to that in hemerythrin.

  7. 57Fe Mössbauer spectroscopy, X-ray single-crystal diffractometry, and electronic structure calculations on natural alexandrite

    NASA Astrophysics Data System (ADS)

    Weber, Sven-Ulf; Grodzicki, Michael; Lottermoser, Werner; Redhammer, Günther J.; Tippelt, Gerold; Ponahlo, Johann; Amthauer, Georg

    2007-09-01

    Natural alexandrite Al2BeO4:Cr from Malyshevo near Terem Tschanka, Sverdlovsk, Ural, Russia, has been characterized by 57Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine oxidation state and location of iron. The sample contains 0.3 wt% of total iron oxide. The 57Fe Mössbauer spectrum can be resolved into three doublets. Two of them with hyperfine parameters typical for octahedrally coordinated high-spin Fe3+ and Fe2+, respectively, are assigned to iron substituting for Al in the octahedral M2-site. The third doublet is attributed to Fe3+ in hematite. Electronic structure calculations in the local spin density approximation are in reasonable agreement with experimental data provided that expansion and/or distortion of the coordination octahedra are presumed upon iron substitution. The calculated hyperfine parameters of Fe3+ are almost identical for the M1 and M2 positions, but the calculated ligand-field splitting is by far too large for high-spin Fe3+ on M1.

  8. 57Fe and Co tracer diffusion in liquid Fe-FeS at 2 and 5 GPa

    NASA Astrophysics Data System (ADS)

    Dobson, David P.

    2000-06-01

    Tracer diffusion in Fe-FeS eutectic melts has been measured at 2.2 and 5 GPa up to 150°C above the solidus using 57Fe and Co thin foils. A new horizontal furnace arrangement for the multi-anvil press is presented, which inhibits convection in the sample and allows diffusion measurements in inviscid materials. The measured diffusivities are identical for 57Fe and Co, and similar to those of pure metals (10 -4-10 -5 cm 2/s). The remarkable agreement between the measured diffusivities at 5 GPa and the value for the inner core boundary derived from ab initio simulations supports the semi-empirical prediction of Poirier [Poirier, J.P., 1988. Transport properties of liquid metals and viscosity of the Earth's core. Geophys. J. 92, 99-105.] and others that transport properties should be constant along a homologous path. The very high activation energies for diffusion ( QD 5 GPa=252±23 kJ/mol) agree well with published values for viscosity ( QV 5 GPa=240±72 kJ/mol) and imply a stronger causational link between metal diffusion and viscosity than previously suggested. That is, viscosity is not solely controlled by sulfur polymerization in the melt.

  9. Line broadening in the 77 K 57Fe-Mössbauer spectra of some ferrous iron-containing medicines

    NASA Astrophysics Data System (ADS)

    Arredondo S., P. I.; Barrero, C. A.; Garcia, K. E.; Greneche, J. M.

    We report line broadening in the 77 K 57Fe Mössbauer spectra of some commercially available medicines based on ferrous sulfates and on ferrous fumarates. While introducing only a single ferrous doublet is required to fit the RT spectra of all samples, on the contrary the line shapes of the 77 K spectra are properly described with two ferrous doublets. We discuss eight different static and dynamic hypotheses as possible physical origins for these two doublets, but finally we propose that the reasons are similar for the ferrous sulfates and for the ferrous fumarates containing medicines, and it can be due to the presence of easily dehydrated and hydrated ferrous compounds. The presence of several hydrated sulfates was confirmed by RT Raman spectroscopy. Possible implications of these results related with the hydrated character by which the active parts of the medicines are fabricated by the pharmaceutical companies are also discussed.

  10. The quantitative determination of FeS2 phases in coal by means of 57Fe Mössbauer spectroscopy

    USGS Publications Warehouse

    Evans, B.J.; King, Hobart M.; Renton, John J.; Stiller, A.

    1990-01-01

    A knowledge of the concentration of pyrite and marcasite in coals can provide important insight into the genesis of coal deposits. Determinations of the relative amounts of pyrite and marcasite by traditional methods of coal analysis are, however, beset with many difficulties. Using 57Fe Mössbauer spectroscopy and a mild chemical treatment with hydrofluoric acid, a technique has been devised for the quantitative determination of the relative concentrations of pyrite and marcasite in samples of whole coals or their low-temperature ashes. The sample preparation procedure is comparable to less accurate methods. Good qualitative agreement has been obtained between ore microscopic and Mössbauer spectroscopic techniques for a series of extensively investigated whole coal samples.

  11. Inelastic scattering in condensed matter with high intensity Moessbauer radiation. Final technical report, December 1, 1989--November 30, 1992

    SciTech Connect

    Yelon, W.B.; Schupp, G.

    1993-02-01

    The QUEGS facility at MURR has produced a number of new results and demonstrated the range of potential applications of high resolution, high intensity Moessbauer scattering. This work has been carried out by both MU and Purdue researchers and includes published results on Na, W, pentadecane, polydimethylsiloxane and other systems, manuscripts submitted on alkali halides (Phys. Rev. B) and accurate Moessbauer lineshape measurements (Phys. Rev. C), and manuscripts in preparation on glycerol, NiAl and Moessbauer spectra obtained by modulating a scattering crystal. Recently, new collaborations have been initiated which will substantially enhance our efforts. These are with W. Steiner (Vienna), G. Coddens (Saclay), and R. D. Taylor (Los Alamos). Steiner is experienced with Fe-57 Moessbauer scattering, while Coddens specializes in quasielastic neutron scattering; both of these areas naturally complement our work. R. D. Taylor has pioneered Moessbauer spectroscopy from the time of its discovery and has already made important contributions to our study of lattice dynamics and superconductivity for lead alloyed with small quantities of tin. At the same time, a significant instrument upgrade is underway, funded in part by the DOE-URIP program.

  12. XRD and {sup 119}Sn Moessbauer spectroscopy characterization of SnSe obtained from a simple chemical route

    SciTech Connect

    Bernardes-Silva, Ana Claudia . E-mail: anaclaudiabs2000@yahoo.com.br; Mesquita, A.F.; Moura de Neto, E.; Porto, A.O. . E-mail: arilzaporto@yahoo.com.br; Ardisson, J.D.; Lameiras, F.S.

    2005-09-01

    Crystalline tin selenide semiconductor was synthesized by a chemical route. Selenium powder reacted with potassium boronhydride, giving a soluble selenium species potassium seleniumhydride. The reaction of potassium seleniumhydride with tin chloride produced crystalline tin selenide, which was characterized by X-ray diffraction, {sup 119}Sn Moessbauer spectroscopy and scanning electronic microscopy. The material was thermally treated, in nitrogen flow, at 300 and 600 deg. C for 2 h and the particle size evolution was studied by X-ray diffraction. The X-ray diffraction and {sup 119}Sn Moessbauer results showed that a mixture of tin oxides and orthorhombic tin selenide was obtained.

  13. Study of C-coated LiFe{sub 0.33}Mn{sub 0.67}PO{sub 4} as positive electrode material for Li-ion batteries

    SciTech Connect

    Perea, A.; Castro, L.; Aldon, L.; Stievano, L.; Dedryvere, R.; Gonbeau, D.; Tran, N.; Nuspl, G.; Breger, J.; Tessier, C.

    2012-08-15

    Commercial C-LiFe{sub 0.33}Mn{sub 0.67}PO{sub 4} positive electrode material has been investigated by {sup 57}Fe Moessbauer Spectroscopy (MS), X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS). The combined use of these experimental techniques provides a better understanding of the electrochemical reaction involved during cycling. {sup 57}Fe MS is very efficient to directly follow oxidation state of Fe in the electrode, and gives surprisingly indirect information on the oxidation state of Mn as observed by XAS and XPS. The electrochemical mechanism is proposed based from in situ and operando investigations using both MS and XAS, and is consistent with XPS surface studies. XPS analysis of the electrodes at the end of charge (4.4 V) reveals enhanced electrode/electrolyte interface reactivity at this high potential. Aging of C-LiFe{sub 0.33}Mn{sub 0.67}PO{sub 4}/Li cells after 50 cycles at 60 Degree-Sign C indicates a rather good electrochemical behavior (low capacity fading) of the electrode material. Both {sup 57}Fe MS and XPS (Mn 2p and Fe 2p) clearly show no modification on Fe and Mn oxidation state compared to fresh electrode confirming the good electrochemical performances. - Graphical abstrct: Quantitative evaluation of the Fe{sup 3+} and Mn{sup 3+} content during the first charge/discharge cycle obtained from K-edge XANES spectra of C-LiFe{sub 0.33}Mn{sub 0.67}PO{sub 4} recorded upon cell operation at RT with C/10 rate. During the charge co-existence of Fe and Mn oxidation is observed between points 2 and 4 of the potential curve. At the end of the charge the cut-off voltage limits the oxidation at about 93%. Highlights: Black-Right-Pointing-Pointer C-LiFe{sub 0.33}Mn{sub 0.67}PO{sub 4} electrode material upon cycling vs. metallic lithium. Black-Right-Pointing-Pointer {sup 57}Fe Moessbauer spectroscopy is a (in)direct probe for Fe(Mn) oxidation state. Black-Right-Pointing-Pointer Both K-Fe and K-Mn edges XAS show a simultaneous

  14. Thermal History of São João Nepomuceno (IVA) Iron Meteorite Inferred from Ganguly's Cooling Rate Model and 57Fe Mössbauer Spectroscopy Data

    NASA Astrophysics Data System (ADS)

    dos Santos, E.; Scorzelli, R. B.; Varela, M. E.

    2016-08-01

    The intracrystalline Fe-Mg distribution in orthopyroxenes, as measured by means of 57Fe Mössbauer spectroscopy and associated to Ganguly’s cooling rate numerical method, are used to infer the thermal history of São João Nepomuceno (IVA) meteorite.

  15. Sensitivity of 57Fe emission Mössbauer spectroscopy to Ar and C induced defects in ZnO

    NASA Astrophysics Data System (ADS)

    Bharuth-Ram, K.; Mølholt, T. E.; Langouche, G.; Geburt, S.; Ronning, C.; Doyle, T. B.; Gunnlaugsson, H. P.; Johnston, K.; Mantovan, R.; Masenda, H.; Naidoo, D.; Ncube, M.; Gislason, H.; Ólafsson, S.; Weyer, G.

    2016-12-01

    Emission Mössbauer Spectroscopy (eMS) measurements, following low fluence (<1012 cm-2) implantation of 57Mn (t 1/2 = 1.5 min.) into ZnO single crystals pre-implanted with Ar and C ions, has been utilized to test the sensitivity of the 57Fe eMS technique to the different types of defects generated by the different ion species. The dominant feature of the Mössbauer spectrum of the Ar implanted ZnO sample was a magnetic hyperfine field distribution component, attributed to paramagnetic Fe3+, while that of the C implanted sample was a doublet attributed to substitutional Fe2+ forming a complex with the C dopant ions in the 2- state at O vacancies. Magnetization measurements on the two samples, on the other hand, yield practically identical m(H) curves. The distinctly different eMS spectra of the two samples display the sensitivity of the probe nucleus to the defects produced by the different ion species.

  16. Theoretical 57Fe Mössbauer spectroscopy: isomer shifts of [Fe]-hydrogenase intermediates.

    PubMed

    Hedegård, Erik Donovan; Knecht, Stefan; Ryde, Ulf; Kongsted, Jacob; Saue, Trond

    2014-03-14

    Mössbauer spectroscopy is an indispensable spectroscopic technique and analytical tool in iron coordination chemistry. The linear correlation between the electron density at the nucleus ("contact density") and experimental isomer shifts has been used to link calculated contact densities to experimental isomer shifts. Here we have investigated relativistic methods of systematically increasing sophistication, including the eXact 2-Component (X2C) Hamiltonian and a finite-nucleus model, for the calculation of isomer shifts of iron compounds. While being of similar accuracy as the full four-component treatment, X2C calculations are far more efficient. We find that effects of spin-orbit coupling can safely be neglected, leading to further speedup. Linear correlation plots using effective densities rather than contact densities versus experimental isomer shift lead to a correlation constant a = -0.294 a0(-3) mm s(-1) (PBE functional) which is close to an experimentally derived value. Isomer shifts of similar quality can thus be obtained both with and without fitting, which is not the case if one pursues a priori a non-relativistic model approach. As an application for a biologically relevant system, we have studied three recently proposed [Fe]-hydrogenase intermediates. The structures of these intermediates were extracted from QM/MM calculations using large QM regions surrounded by the full enzyme and a solvation shell of water molecules. We show that a comparison between calculated and experimentally observed isomer shifts can be used to discriminate between different intermediates, whereas calculated atomic charges do not necessarily correlate with Mössbauer isomer shifts. Detailed analysis reveals that the difference in isomer shifts between two intermediates is due to an overlap effect.

  17. Moessbauer assessment of cation disorder in columbite-tantalite minerals

    SciTech Connect

    Augsburger, M.S.; Pedregosa, J.C.; Sosa, G.M.; Mercader, R.C.

    1999-03-01

    The authors have used X-ray diffraction and Moessbauer spectroscopy to investigate the cationic disorder between crystallographic sites of a columbite-tantalite series of pegmatites. The X-ray results show that the pegmatites have different degrees of crystallographic disorder according to the quarries where the samples come from. Moessbauer spectra allow us to distinguish two Fe{sup 2+} different sites. A simple model assuming equal f-factors and occupation probabilities both for Fe and Mn has been used to turn the relative populations for Fe yielded by Moessbauer spectroscopy into effective site occupancy of the 2+ ions. A well-known empirical formula applied to X-ray results to obtain cationic disorder has been found to correlate within experimental errors with the percentage of cationic ordering obtained by Moessbauer spectroscopy.

  18. Moessbauer search for ferric oxide phases in lunar materials and simulated lunar materials

    NASA Technical Reports Server (NTRS)

    Forester, D. W.

    1973-01-01

    Moessbauer studies were carried out on lunar fines and on simulated lunar glasses containing magnetic-like precipitates with the primary objective of determining how much, if any, ferric oxide is present in the lunar soils. Although unambiguous evidence of lunar Fe(3+) phases was not obtained, an upper limit was estimated from different portions of the Moessbauer spectra to be between 0.1 and 0.4 wt.% (as Fe3O4). A smaller than 62 microns fraction of 15021,118 showed 0.5 wt.% ferromagnetic iron at 300 K in as-returned condition. After heating to 650 C in an evacuated, sealed quartz tube for 1400 hours, the same sample exhibited 1 wt.% ferromagnetic iron at room temperature. An accompanying decrease in excess absorption area near zero velocity was noted. Thus, the result of the vacuum heat treatment was to convert fine grained iron to larger particles, apparently without the oxidation effects commonly reported.

  19. Moessbauer analysis of heat affected zones of an SA 508 steel weld

    SciTech Connect

    Kwon, S.J.; Oh, S.J.; Kim, S.; Lee, S.; Kim, J.H.

    1998-12-18

    Microstructure of a heat affected zone (HAZ) in a weld is influenced by many factors such as chemical composition, welding condition, and peak temperature. It is more complex under multi-pass welding because of the repeated heat input. For the analysis of the HAZ microstructure, optical microscope, electron microscope, and X-ray diffraction techniques have been widely used. However, their application is limited since they can hardly make quantitative analysis of HAZ where numerous phases such as martensite, bainite, ferrite, pearlite, austenite, and carbides are co-existing. Moessbauer spectroscopy, in such a case, is particularly useful due to the capability of quantitative analysis on the fraction of each phase. In this study, phases present in the HAZ of an SA 508 steel were identified, and their fractions were quantitatively determined by Moessbauer spectroscopy in conjunction with microscopic observations.

  20. Moessbauer search for ferric oxide phases in lunar materials and simulated lunar materials

    NASA Technical Reports Server (NTRS)

    Forester, D. W.

    1973-01-01

    Moessbauer studies were carried out on lunar fines and on simulated lunar glasses containing magnetic-like precipitates with the primary objective of determining how much, if any, ferric oxide is present in the lunar soils. Although unambiguous evidence of lunar Fe(3+) phases was not obtained, an upper limit was estimated from different portions of the Moessbauer spectra to be between 0.1 and 0.4 wt.% (as Fe3O4). A smaller than 62 microns fraction of 15021,118 showed 0.5 wt.% ferromagnetic iron at 300 K in as-returned condition. After heating to 650 C in an evacuated, sealed quartz tube for 1400 hours, the same sample exhibited 1 wt.% ferromagnetic iron at room temperature. An accompanying decrease in excess absorption area near zero velocity was noted. Thus, the result of the vacuum heat treatment was to convert fine grained iron to larger particles, apparently without the oxidation effects commonly reported.

  1. Gamma scattering in condensed matter with high intensity Moessbauer radiation. Final technical progress report, January 16, 1993--January 15, 1996

    SciTech Connect

    1997-06-01

    Progress is reported on work with high intensity radiation. Moessbauer radioisotopes of exceptional high intensity have been the source of photons for most experiments. Topics include lattice dynamics, studies of glass forming liquids, and line-shape and it`s role in finding materials and nuclear parameters.

  2. Iron-oxide aerogel and xerogel catalyst formulations: characterization by 57Fe Mössbauer and XAFS spectroscopies.

    PubMed

    Huggins, Frank E; Bali, Sumit; Huffman, Gerald P; Eyring, Edward M

    2010-06-01

    Iron in various iron-oxide aerogel and xerogel catalyst formulations (> or =85% Fe(2)O(3); < or =10% K, Co, Cu, or Pd) developed for possible use in Fischer-Tropsch synthesis (FTS) or the water-gas-shift (WGS) reaction has been examined by (57)Fe Mössbauer spectroscopy. The seventeen samples consisted of both as-prepared and calcined aerogels and xerogels and their products after use as catalysts for FTS or the WGS reaction. Complementary XAFS spectra were obtained on the occurrence of the secondary elements in some of the same materials. A broad, slightly asymmetric, two-peak Mössbauer spectrum was obtained from the different as-prepared and calcined catalyst formulations in the majority of cases. Such spectra could only be satisfactorily fit with three quadrupole doublet components, but no systematic trends in the isomer shift and quadrupole splitting parameters and area ratios of the individual components could be discerned that reflected variations in the composition or preparation of the aerogel or xerogel materials. However, significant reductions were noted in the Mössbauer effective thickness (recoilless absorption effect per unit mass of iron) parameter, chi(eff)/g, determined at room temperature, for aerogels and xerogels compared to bulk iron oxides, reflecting the openness and lack of rigidity of the aerogel and xerogel structures. Mössbauer measurements for two aerogels over the range from 15 to 292K confirmed the greatly diminished nature of this parameter at room temperature. Major increases in the effective thickness parameter were observed when the open structure of the aerogel or xerogel collapsed during calcination resulting in the formation of iron oxides (hematite, spinel ferrite). Similar structural changes were indicated by increases in this parameter after use of iron-oxide aerogels as catalysts for FTS or the WGS reaction, during which the iron-oxide aerogel was converted to a mixture of nonstoichiometric magnetite and the Hägg carbide

  3. Moessbauer studies in Zn(2+)0.3 Mn(2+)0.7 Mn(3+) (2-y) Fe(3+) (2-y) O4

    NASA Technical Reports Server (NTRS)

    Gupta, R. G.; Mendiratta, R. G.; Escue, W. T.

    1975-01-01

    The Mossbauer effect has proven to be effective in the study of nuclear hyperfine interactions. Ferrite systems having the formula (Zn(2+)0.3)(Mn(2+)0.7)(Mn(3+)y)(Fe(3+)2-y)(O4) were prepared and studied. These systems can be interpreted as mangacese-doped zinc and a part of iron ions. A systematic study of these systems is presented to promote an understanding of their microstructure for which various theories were proposed.

  4. Fe-implanted 6H-SiC: Direct evidence of Fe{sub 3}Si nanoparticles observed by atom probe tomography and {sup 57}Fe Mössbauer spectroscopy

    SciTech Connect

    Diallo, M. L.; Fnidiki, A. Lardé, R.; Cuvilly, F.; Blum, I.; Lechevallier, L.; Debelle, A.; Thomé, L.; Viret, M.; Marteau, M.; Eyidi, D.; Declémy, A.

    2015-05-14

    In order to understand ferromagnetic ordering in SiC-based diluted magnetic semiconductors, Fe-implanted 6H-SiC subsequently annealed was studied by Atom Probe Tomography, {sup 57}Fe Mössbauer spectroscopy and SQUID magnetometry. Thanks to its 3D imaging capabilities at the atomic scale, Atom Probe Tomography appears as the most suitable technique to investigate the Fe distribution in the 6H-SiC host semiconductor and to evidence secondary phases. This study definitely evidences the formation of Fe{sub 3}Si nano-sized clusters after annealing. These clusters are unambiguously responsible for the main part of the magnetic properties observed in the annealed samples.

  5. Variable-Temperature Tin-119m Moessbauer Study of the Chlorodimethyltin (IV) Derivatives of L-Cysteine and DL-Penicillamine.

    DTIC Science & Technology

    1981-06-15

    TECHNICAL REPORT No. 31 ("!. Variable-Temperature Tin-119m M0ssbauer Study of the Chlorodimethyltin(IV) Derivatives of L-Cysteine and DL- Penicillamine K...and DL- Penicillamine -6. PERFORMING ORG. REPO’T NUMBER 7. AUTHOR(,) ... /- . CONTRACT OR GRANT NU AUER(,) K olloy an4_J.J./Zuckerman I N,,0 / .4-77-C...Cysteine, Penicillamine , M?5ssbauer spectroscopy, Hydrogen bonding, Variable-Temperature Mbssbauer, Tin 20. ABSTRACT (Continue an reverse side If neceeesty

  6. Mineralogical and Geochemical Analyses of Antarctic Lake Sediments: A Reflectance and Moessbauer Spectroscopy Study with Applications for Remote Sensing on Mars

    NASA Technical Reports Server (NTRS)

    Froeschl, Heinz; Lougear, Andre; Trautwein, Alfred X.; Newton, Jason; Doran, Peter T.; Koerner, Wilfried; Koeberl, Christian; Bishop, Janice (Technical Monitor); DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    Lakebottom sediments from the Dry Valleys region of Antarctica have been analyzed here in order to study the influence of water chemistry on the mineralogy and geochemistry of these sediments, as well as to evaluate techniques for remote spectral identification of potential biomarker minerals on Mars. Lakes from the Dry Valleys region of Antarctica have been investigated as possible analogs for extinct lake environments on early Mars. Sediment cores were collected in the present study from perennially ice-covered Lake Hoare in the Taylor Valley. These sediments were taken from a core in an oxic region of the lake and another core in an anoxic zone. Differences between the two cores were observed in the sediment color, Fe(II)/Fe(III) ratio, the presence of pyrite, the abundance of Fe, S and some trace elements, and the C, N and S isotope fractionation patterns. The results of visible-infrared reflectance spectroscopy (0.3-25 microns) Mossbauer spectroscopy (77 and 4 K) and X-ray diffraction are combined to determine the mineralogy and composition of these samples. The sediments are dominated by plagioclase, K-feldspar, quartz and pyroxene. Algal mats grow on the bottom of the lake and organic material has been found throughout the cores. Calcite is abundant in some layers of the aerobic core (shallow region) and pyrite is abundant in some layers of the anaerobic core (deep region). Analysis of the spectroscopic features due to organics and carbonates with respect to the abundance of organic C and carbonate contents was performed in order to select optimal spectral bands for remote identification of these components in planetary regoliths. Carbonate bands near 4 and 6.8 microns (approx.2500 and 1500/cm) were detected for carbonate abundances as low as 0.1 wt.% CO2. Organic features at 3.38, 3.42 and 3.51 microns (2960, 2925 and 2850/cm) were detected for organic C abundances as low as 0.06 wt.% C. The d13C trends show a more complex organic history for the anaerobic

  7. Moessbauer Spectroscopy of Martian and Sverrefjell Carbonates

    NASA Technical Reports Server (NTRS)

    Agresti, David G.; Morris, Richard V.

    2011-01-01

    Mars, in its putative "warmer, wetter: early history, could have had a CO2 atmosphere much denser than its current value of <10 mbar. The question of where all this early CO2 has gone has long been debated. Now, several instruments on Mars Exploration Rover (MER) Spirit, including its Moessbauer spectrometer MIMOS II, have identified Mg-Fe carbonate in rock outcrops at Comanche Spur in the Columbia Hills of Gusev Crater. With this finding, carbonate cements in volcanic breccia collected on Sverrefjell Volcano on Spitzbergen Island in the Svalbard Archipelago (Norway) during the AMASE project are mineralogical and possible process analogues of the newly discovered martian carbonate. We report further analyses of Mossbauer spectra from Comanche Spur and discuss their relationship to Mossbauer data acquired on Sverrefjell carbonates. The spectra were velocity calibrated with MERView and fit using MERFit. Instead of the "average temperature" Comanche spectrum (data from all temperature windows summed), we refit the Comanche data for QS within each temperature window, modeling as doublets for Fe2+(carbonate), Fe2+(olivine), and Fe3+(npOx). The temperature dependences of QS for the Comanche carbonate and for a low-Ca carbonate from Chocolate Pots in Yellowstone National Park (YNP) are shown; they are the same within error. For Comanche carbonate summed over 210-270 K, (CS, QS) = (1.23, 1.95) mm/s. The value of QS for Sverrefjell carbonate at 295 K, (CS, QS) = (1.25, 1.87) mm/s, is also plotted, and the plot shows that the QS for the Sverrefjell carbonate agrees within error with the Comanche data extrapolated to 295 K. This agreement is additional evidence that the Sverrefjell carbonates are Mossbauer analogues for the Comanche carbonates, and that both carbonates might have precipitated from solutions that became carbonate rich by passing through buried carbonate deposits.

  8. Moessbauer spectroscopy at pressures up to 40 GPa

    SciTech Connect

    Taylor, R.D.; Pasternak, M.P.

    1991-11-20

    Mossbauer spectroscopy (MS) is a viable ``non-contact`` technique applicable to high-pressure, diamond anvil cells (DAC) with samples containing a wide variety of the elements suitable for MS. The convenience and simplicity of diamond anvil cells as a means to obtain static high pressures even into the megabar regime has resulted in a renewed interest in pressure as a complement to the usual physical measurements. However, the required small sample size and the difficulty of communicating with the sample leave only x-ray and optical spectroscopy as the readily available tools. Mossbauer spectroscopy which involves recoil-free, low-energy {gamma} rays, provides a powerful additional technique to study a myriad of physical properties in a DAC. MS concerns a particular isotope and can provide local information on phase changes and hysteresis, isomer shifts, valence, bonding, magnetic and quadrupolar interactions, lattice dynamics, and multiple sites. The Mossbauer effect has been seen in about a hundred isotopic transitions in about forty different elements; many are suitable for DAC-MS, most notably {sup 57}Fe, {sup 119}Sn, {sup 121}Sb, {sup 125}Te, {sup 129}I, {sup 149}Sn, {sup 151}Eu, {sup 161}Dy, {sup 1976}Au, and {sup 237}Np. Since the information available from MS is obtained from analyzing the precise energy profile of the Mossbauer {gamma} ray from a source/absorber combination, no contacts or difficult coupling to the DAC are required. We review a number of salient features of the DAC-MS method and present some examples, including new work on FeI{sub 2}.

  9. Different 57Fe microenvironments in the nanosized iron cores in human liver ferritin and its pharmaceutical analogues on the basis of temperature dependent Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Oshtrakh, M. I.; Alenkina, I. V.; Klencsár, Z.; Kuzmann, E.; Semionkin, V. A.

    2017-02-01

    Mössbauer spectra of human liver ferritin and its pharmaceutical analogues Ferrum Lek and Maltofer® measured at various temperatures within the range of 295-83 K were fitted using five quadrupole doublets related to different 57Fe microenvironments in various layers/regions of the ferrihydrite and akaganéite iron cores. The observed anomalous temperature dependences of some Mössbauer parameters were considered as a result of low temperature structural rearrangements in different layers/regions in the iron core.

  10. 57Fe Mössbauer, SEM/EDX, p-XRF and μ-XRF studies on a Dutch painting

    NASA Astrophysics Data System (ADS)

    Lehmann, R.; Schmidt, H.-J.; Costa, B. F. O.; Blumers, M.; Sansano, A.; Rull, F.; Wengerowsky, D.; Nürnberger, F.; Maier, H. J.; Klingelhöfer, G.; Renz, F.

    2016-12-01

    The painting of a rich Jewish merchant "Bildnis eines jüdischen Kaufmanns" from the Netherlands is dated presumably to the 16th century. After a vivid historical background, i.e. robbed by the Nazis by order of Hermann Göring, it was recently discovered on an Austrian flea market. Different analysis methods were combined to identify the time of the production of this historically interesting looted art. Non-destructive MIMOS II Fe-57 Mössbauer spectroscopy was utilised for mesurements in selected spots. This mainly revealed haematite ( α-Fe2O3) in the red curtain. In spots of the brown jacket Mössbauer spectra indicated the presence of mainly Iron(III) in super-paramagnetic oxide or oxide-hydroxide. Consecutively SEM measurements revealed a restoration by partly over-painting. The elementary composition of the pigments was examined by a portable-X-ray fluorescence. μ-XRF analysis for element distribution at different areas was performed. The look into a crack showed Zinc-white at the bottom of the crack. Traces of Titanium-white could be found within some locations on the surface of the painting. In terms of provenance of the artwork, the presence of Zink-white suggests that the painting was painted around the 19th century. Titanium-white indicates a reconstruction during the 20th century, approximately between 1917 and 1958.

  11. Monte Carlo simulation of dose distribution in water around 57Fe3O4 magnetite nanoparticle in the nuclear gamma resonance condition

    NASA Astrophysics Data System (ADS)

    Gabbasov, R.; Polikarpov, M.; Safronov, V.; Sozontov, E.; Yurenya, A.; Panchenko, V.

    2016-12-01

    In this work was proposed a new radiotherapy enhancement method consisting of the administration of magnetic nanoparticles into the cells with further irradiation with a gamma-ray beam. As a result, adjusting the energy distribution of a gamma-ray beam and 57Fe abundance it is possible to achieve an extremely intensive electron emission because of a nuclear resonance. The produced conversion and Auger electrons can be used as an effective tool for DNA lesions production. We developed a Monte Carlo model for an electron and gamma emission by 57Fe nucleus using the Geant4 program package. The parameters of a resonant absorption were taken from Mössbauer spectra of magnetite nanoparticles synthesized for the administration into live cells. The space distribution of the radiation dose showed an increase in the dose of 2-2.5 times in the case of the natural abundance and more than 50 times in the case of the 66 % enrichment of the nanoparticles.

  12. The Miniaturized Moessbauer Spectrometers MIMOS II on MER: Four Years of Operation - A Summary

    NASA Technical Reports Server (NTRS)

    Fleischer, I.; Klingelhoefer, G.; Morris, R. V.; Rodionov, D.; Blumers, M.; Bernhardt, B.; Schroeder, C.; Ming, D. W.; Yen, A. S.; Cohen, B. A.; McCoy, T. J.; Mittlefehldt, D. W.; Schmidt, M. E.; Girones Lopez, J.; Studlek, G.; Brueckner, J.; Gellert, R.; d'Uston, C.

    2008-01-01

    The two Miniaturized Moessbauer Spectrometers (MIMOS II) on board the two Mars Exploration Rovers Spirit and Opportunity have now been collecting important scientific data for more than four years. The spectrometers provide information about Fe-bearing mineral phases and determine Fe oxidation states. The total amount of targets analized exceeds 600, the total integration time exceeds 260 days for both rovers. Since landing, more than five half-lives of the Co-57 MB sources have past (intensity at the time of landing approx. 150 mCi). Current integration times are about 50 hours in order to achieve reasonable statistics as opposed to 8 hours at the beginning of the mission. In total, 13 different mineral phases were detected: Olivine, pyroxene, hematite, magnetite and nanophase ferric oxide were detected at both landing sites. At Gusev, ilmenite, goethite, a ferric sulfate phase and a yet unassigned phase (in the rock Fuzzy Smith) were detected. At Meridiani, jarosite, metallic iron in meteoritic samples (kamacite), troilite, and an unassigned ferric phase were detected. Jarosite and goethite are of special interest, as these minerals are indicators for water activity. In this abstract, an overview of Moessbauer results will be given, with a focus on data obtained since the last martian winter. The MER mission has proven that Moessbauer spectroscopy is a valuable tool for the in situ exploration of extraterrestrial bodies and for the study of Febearing samples. The experience gained through the MER mission makes MIMOS II a obvious choice for future missions to Mars and other targets. Currently, MIMOS II is on the scientific payload of two approved future missions: Phobos Grunt (Russian Space Agency; 2009) and ExoMars (European Space Agency; 2013).

  13. Speciation of triphenyltin compounds using Moessbauer spectroscopy. Final report

    SciTech Connect

    Eng, G.

    1993-11-01

    Organotin compounds have been used widely as the active agent in antifouling marine paints. Organotin compounds, i.e., tributyltin compounds (TBTs) and triphenyltin compounds (TPTs) have been found to be effective in preventing the unwanted attachment and development of aquatic organisms such as barnacles, sea grass and hydroids on ships, hulls and underwater surfaces. However, these organotin compounds have been found to be toxic to non-targeted marine species as well. While speciation of tributyltins in environmental water systems has received much attention in the literature, little information concerning the speciation of triphenyltins is found. Therefore, it would be important to study the fate of TPTs in the aquatic environment, particularly in sediments, both oxic and anoxic, in order to obtain speciation data. Since marine estuaries consist of areas with varying salinity and pH, it is important to investigate the speciation of these compounds under varying salinity conditions. In addition, evaluation of the speciation of these compounds as a function of pH would give an insight into how these compounds might interact with sediments in waters where industrial chemical run-offs can affect the pH of the estuarine environment. Finally, since organotins are present in both salt and fresh water environments, the speciation of the organotins in seawater and distilled water should also be studied. Moessbauer spectroscopy would provide a preferred method to study the speciation of triphenyltins as they leach from marine paints into the aquatic environment. Compounds used in this study are those triphenyltin compounds that are commonly incorporated into marine paints such as triphenyltin fluoride (TPTF), triphenyltin acetate (TPTOAc), triphenyltin chloride (TPTCl) and triphenyltin hydroxide (TPTOH).

  14. Identification of Iron-Bearing Phases on the Martian Surface and in Martian Meteorites and Analogue Samples by Moessbauer Spectroscopy

    NASA Technical Reports Server (NTRS)

    Klingelhoefer, G.; Agresti, D. G.; Schroeder, C.; Rodionov, D.; Yen, A.; Ming, Doug; Morris, Richard V.

    2007-01-01

    The Moessbauer spectrometers on the Mars Exploration Rovers (MER) Spirit (Gusev Crater) and Opportunity (Meridiani Planum) have each analyzed more than 100 targets during their ongoing missions (>1050 sols). Here we summarize the Fe-bearing phases identified to date and compare the results to Moessbauer analyses of martian meteorites and lunar samples. We use lunar samples as martian analogues because some, particularly the low-Ti Apollo 15 mare basalts, have bulk chemical compositions that are comparable to basaltic martian meteorites [1,2]. The lunar samples also provide a way to study pigeonite-rich samples. Pigeonite is a pyroxene that is not common in terrestrial basalts, but does often occur on the Moon and is present in basaltic martian meteorites

  15. Moessbauer Spectroscopy on the Martian Surface: Constraints on Interpretation of MER Data

    NASA Technical Reports Server (NTRS)

    Dyar, M. D.; Schaefer, M. W.

    2003-01-01

    Moessbauer spectrometers will be used on martian landers and rovers to identify and quantify relative amounts of Fe-bearing minerals, as well as to determine their Fe(3+)/Fe(2+) ratios, allowing more realistic modeling of martian mineralogy and evolution. However, derivation of mineral modes, Fe(3+)/Fe(2+) ratios, and phase identification via Moessbauer spectroscopy (MS) does have limitations. We discuss here the exciting potential of MS for remote planetary exploration, as well as constraints on interpretation of remote Moessbauer data.

  16. Moessbauer Mineralogy on the Moon: The Lunar Regolith

    NASA Technical Reports Server (NTRS)

    Morris, Richard V.; Korotev, Randy L..; Shelfer, Tad D.; Klingelhoefer, Goestar

    1997-01-01

    A first-order requirement for spacecraft missions that land on solid planetary objects is instrumentation for mineralogical analyses. For purposes of providing diagnostic information about naturally-occurring materials, the element iron is particularly important because it is abundant and multivalent. Knowledge of the oxidation state of iron and its distribution among iron-bearing mineralogies tightly constrains the types of materials present and provides information about formation and modification (weathering) processes. Because Moessbauer spectroscopy is sensitive to both the valence of iron and its local chemical environment, the technique is unique in providing information about both the relative abundance of iron-bearing phases and oxidation state of the iron. The Moessbauer mineralogy of lunar regolith samples (primarily soils from the Apollo 16 and 17 missions to the Moon) were measured in the laboratory to demonstrate the strength of the technique for in situ mineralogical exploration of the Moon. The regolith samples were modeled as mixtures of five iron-bearing phases: olivine, pyroxene, glass, ilmenite, and metal. Based on differences in relative proportions of iron associated with these phases, volcanic ash regolith can be distinguished from impact-derived regolith, impact-derived soils of different geologic affinity (e.g., highlands, maria) can be distinguished on the basis of their constituent minerals, and soil maturity can be estimated. The total resonant absorption area of the Moessbauer spectrum can be used to estimate total FeO concentrations.

  17. Moessbauer Characterization of Magnetite/Polyaniline Magnetic Nanocomposite

    SciTech Connect

    Rodriguez, Anselmo F. R.; Faria, Fernando S. E. D. V.; Lopez, Jorge L.; Mesquita, Antonio G. G.; Coaquira, Jose A. H.; Oliveira, Aderbal C.; Morais, Paulo C.; Azevedo, Ricardo B.; Araujo, Ana C. V. de; Alves, Severino Jr.; Azevedo, Walter M. de

    2010-12-02

    Aniline surface coated Fe{sub 3}O{sub 4} nanoparticles have been successfully synthesized by UV irradiation varying the time and the acid media (HCl, HNO{sub 3}, or H{sub 2}SO{sub 4}). The synthesized material represents a promising platform for application in nerve regeneration. XRD patterns are consistent with the crystalline structure of magnetite. Nevertheless, for UV irradiation times longer than 2 h, extra XRD lines reveal the presence of goethite. The mean crystallite size of uncoated particles is estimated to be 25.4 nm, meanwhile that size is reduced to 19.9 nm for the UV irradiated sample in HCl medium for 4 h. Moessbauer spectra of uncoated nanoparticles reveal the occurrence of thermal relaxation at room temperature, while the 77 K-Moessbauer spectrum suggests the occurrence of electron localization effects similar to that expected in bulk magnetite. The Mossbauer spectra of UV irradiated sample in HCl medium during 4 h, confirms the presence of the goethite phase. For this sample, the thermal relaxation is more evident, since the room temperature spectrum shows larger spectral area for the nonmagnetic component due to the smaller crystallite size. Meanwhile, the 77 K-Moessbauer spectrum suggests the absence of the electron localization effect above 77 K.

  18. Moessbauer measurements of microstructural change in aged duplex stainless steel

    SciTech Connect

    Kirihigashi, A.; Sakamoto, N.; Yamaoka, T.; Nasu, S.

    1995-08-01

    A duplex stainless steel (ASME SA351 CF8M) has usually been manufactured by a continuous casting technique. It consists of a paramagnetic austenite phase and a ferromagnetic ferrite phase. It has been known that the ferrite phase decomposition occurs in this steel after aging between 300 and 450 C. As a result of phase decomposition, a Fe-rich phase and a Cr-rich phase are produced in the ferrite phase. It is difficult to detect the phase decomposition even by not only optical microscopy but also transmission electron microscopy, since the decomposed structure is very fine. However, Moessbauer measurements that can detect the magnetic hyperfine field of magnetic substance may detect the microstructural change. An averaged magnetic hyperfine field increases in the ferrite phase, due to the production of the Fe-rich phase which has high magnetic hyperfine field. Therefore, the authors investigated the phase decomposition of the duplex stainless steel caused by aging, utilization Moessbauer spectroscopy which has capability of detecting this structural change in the atomic level quantitatively. The authors also investigated the potential of backscattering Moessbauer method for NDE technique.

  19. Nuclear resonant scattering measurements on {sup 57}Fe by multichannel scaling with a 64-pixel silicon avalanche photodiode linear-array detector

    SciTech Connect

    Kishimoto, S. Haruki, R.; Mitsui, T.; Yoda, Y.; Taniguchi, T.; Shimazaki, S.; Ikeno, M.; Saito, M.; Tanaka, M.

    2014-11-15

    We developed a silicon avalanche photodiode (Si-APD) linear-array detector for use in nuclear resonant scattering experiments using synchrotron X-rays. The Si-APD linear array consists of 64 pixels (pixel size: 100 × 200 μm{sup 2}) with a pixel pitch of 150 μm and depletion depth of 10 μm. An ultrafast frontend circuit allows the X-ray detector to obtain a high output rate of >10{sup 7} cps per pixel. High-performance integrated circuits achieve multichannel scaling over 1024 continuous time bins with a 1 ns resolution for each pixel without dead time. The multichannel scaling method enabled us to record a time spectrum of the 14.4 keV nuclear radiation at each pixel with a time resolution of 1.4 ns (FWHM). This method was successfully applied to nuclear forward scattering and nuclear small-angle scattering on {sup 57}Fe.

  20. Search for 14.4 keV solar axions emitted in the M1-transition of 57Fe nuclei with CAST

    NASA Astrophysics Data System (ADS)

    CAST Collaboration; Andriamonje, S.; Aune, S.; Autiero, D.; Barth, K.; Belov, A.; Beltrán, B.; Bräuninger, H.; Carmona, J. M.; Cebrián, S.; Collar, J. I.; Dafni, T.; Davenport, M.; Di Lella, L.; Eleftheriadis, C.; Englhauser, J.; Fanourakis, G.; Ferrer-Ribas, E.; Fischer, H.; Franz, J.; Friedrich, P.; Geralis, T.; Giomataris, I.; Gninenko, S.; Gómez, H.; Hasinoff, M.; Heinsius, F. H.; Hoffmann, D. H. H.; Irastorza, I. G.; Jacoby, J.; Jakovčić, K.; Kang, D.; Königsmann, K.; Kotthaus, R.; Krcmar, M.; Kousouris, K.; Kuster, M.; Lakić, B.; Lasseur, C.; Liolios, A.; Ljubičić, A.; Lutz, G.; Luzón, G.; Miller, D.; Morales, J.; Ortiz, A.; Papaevangelou, T.; Placci, A.; Raffelt, G.; Riege, H.; Rodríguez, A.; Ruz, J.; Savvidis, I.; Semertzidis, Y.; Serpico, P.; Stewart, L.; Vieira, J.; Villar, J.; Vogel, J.; Walckiers, L.; Zioutas, K.

    2009-12-01

    We have searched for 14.4 keV solar axions or more general axion-like particles (ALPs), that may be emitted in the M1 nuclear transition of 57Fe, by using the axion-to-photon conversion in the CERN Axion Solar Telescope (CAST) with evacuated magnet bores (Phase I). From the absence of excess of the monoenergetic X-rays when the magnet was pointing to the Sun, we set model-independent constraints on the coupling constants of pseudoscalar particles that couple to two photons and to a nucleon gaγ|-1.19gaN0+gaN3| < 1.36 × 10-16 GeV-1 for ma < 0.03 eV at the 95% confidence level.

  1. Nuclear resonant scattering measurements on (57)Fe by multichannel scaling with a 64-pixel silicon avalanche photodiode linear-array detector.

    PubMed

    Kishimoto, S; Mitsui, T; Haruki, R; Yoda, Y; Taniguchi, T; Shimazaki, S; Ikeno, M; Saito, M; Tanaka, M

    2014-11-01

    We developed a silicon avalanche photodiode (Si-APD) linear-array detector for use in nuclear resonant scattering experiments using synchrotron X-rays. The Si-APD linear array consists of 64 pixels (pixel size: 100 × 200 μm(2)) with a pixel pitch of 150 μm and depletion depth of 10 μm. An ultrafast frontend circuit allows the X-ray detector to obtain a high output rate of >10(7) cps per pixel. High-performance integrated circuits achieve multichannel scaling over 1024 continuous time bins with a 1 ns resolution for each pixel without dead time. The multichannel scaling method enabled us to record a time spectrum of the 14.4 keV nuclear radiation at each pixel with a time resolution of 1.4 ns (FWHM). This method was successfully applied to nuclear forward scattering and nuclear small-angle scattering on (57)Fe.

  2. Search for 14.4 keV solar axions emitted in the M1-transition of {sup 57}Fe nuclei with CAST

    SciTech Connect

    Andriamonje, S.; Aune, S.; Dafni, T.; Ferrer-Ribas, E.; Autiero, D.; Barth, K.; Davenport, M.; Lella, L. Di; Belov, A.; Beltrán, B.; Carmona, J.M.; Cebrián, S.; Bräuninger, H.; Englhauser, J.; Friedrich, P.; Collar, J.I.; Eleftheriadis, C.; Fanourakis, G.; Fischer, H.; Franz, J.; Collaboration: CAST collaboration; and others

    2009-12-01

    We have searched for 14.4 keV solar axions or more general axion-like particles (ALPs), that may be emitted in the M1 nuclear transition of {sup 57}Fe, by using the axion-to-photon conversion in the CERN Axion Solar Telescope (CAST) with evacuated magnet bores (Phase I). From the absence of excess of the monoenergetic X-rays when the magnet was pointing to the Sun, we set model-independent constraints on the coupling constants of pseudoscalar particles that couple to two photons and to a nucleon g{sub aγ}|−1.19g{sub aN}{sup 0}+g{sub aN}{sup 3}| < 1.36 × 10{sup −16} GeV{sup −1} for m{sub a} < 0.03 eV at the 95% confidence level.

  3. Site characterization of 57Fe implanted in epitaxial thin films of Y 1Ba 2Cu 3O 7-δ by conversion electron Mössbauer technique

    NASA Astrophysics Data System (ADS)

    Vedawyas, M.; Bhagwat, A.; Marest, G.; Jaffrezic, H.

    1997-02-01

    Identification of Fe sites in doped Y 1Ba 2Cu 3O 7-δ thin films has been done using conversion electron Mössbauer spectroscopy (CEMS). We have used the ion implantation technique to achieve very a low concentration of 57Fe in Y 1Ba 2(Cu (1- x) Fe x) 3O 7-δ thin films with 0.01 < x < 0.05. The preferences of the populated Cu sites and their evolution with thermal treatment is discussed in detail. The Fe ions occupy predominantly square pyramidal chain sites and quasi-octahedral plane sites; this has not been observed for Y 1Ba 2(Cu (1- x) Fe x) 3O 7-δ prepared via the normal thermodynamic route. Some phenomenological mechanisms for the differences in the observations is discussed.

  4. Galvanostatic charge-discharge tests, 57Fe and 119Sn Mössbauer and XRD measurements on novel Sn-Ni-Fe electrodeposits

    NASA Astrophysics Data System (ADS)

    Lak, G. B.; Kuzmann, E.; El-Sharif, M.; Chisholm, C. U.; Stichleutner, S.; Homonnay, Z.; Sziráki, L.

    2013-04-01

    Novel Sn-Ni-Fe ternary alloys were successfully deposited by pulse plating technique from an electrolyte based on sodium gluconate which acts as a complexing agent. XRD results revealed the predominantly amorphous character for the majority of the deposits. 57Fe and 119Sn conversion electron Mössbauer spectroscopy indicated the formation of a paramagnetic amorphous alloy using a short on-pulse duration and where the Fe content was less than 22 wt.%. Galvanostatic charge-discharge tests of the novel Sn-Ni-Fe deposits were carried out in a model Li-ion cell and indicated that the Sn-Ni-Fe alloys have potential as an electrode material.

  5. Electronic structure properties of neptunium intermetallics under pressure from Moessbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Kalvius, G. M.; Potzel, W.; Zwirner, S.; Gal, J.; Nowik, I.

    1994-10-01

    Electronic structure properties of neptunium intermetallics obtained by the 60 keV Moessbauer resonance in Np-237 in the pressure range up to 9 GPa and at temperatures from 1.5 K to about 150 K together with X-ray determinations of the bulk modulus are discussed. Samples of the NaCl compounds NpX, the Laves phases NpX2 and the AuCu3 materials NpX3 as well as the tetragonal series NpX2S2 have been studied. The volume coefficients of magnetic moment and magnetic transition temperature allow the classification in terms of 5f bandwidth arising either from 5f-5f overlap or hybridization with ligand s, p, or d electrons. The pressure-temperature magnetic phase diagram of some of these compounds has also been investigated. In NpGa3 and NpIn3 we find a preference for ferromagnetic order under reduced volume. Finally we address the question of crystal field interactions and show that even in a somewhat delocalized case (NpAl2) they are decisive in determining the high pressure Moessbauer spectra.

  6. Determination of the Moessbauer parameters of rare-earth nitroprussides: Evidence for new light-induced magnetic excited state (LIMES) in nitroprussides

    SciTech Connect

    Rusanov, V.; Stankov, S.; Ahmedova, A.; Trautwein, A.X.

    2009-05-15

    Nitroprussides of the rare-earth elements and some mixed rare-earth-sodium nitroprussides are studied by Moessbauer spectroscopy at ambient and lower temperatures. The high precision Moessbauer measurements reveal fine changes in the electronic configurations of the nitroprusside anions. A small increase of the quadrupole splitting reveals charge polarization effects in the nitroprusside anion caused by the oblate or prolate shape of the rare-earth ion and the lanthanide contraction. Despite the very large magnetic moment of holmium a magnetic phase transition is not observed down to 300 mK. The population of the metastable states SI and SII are evidenced in europium and scandium nitroprussides, and most likely they can be populated in all rare-earth nitroprussides. No distinct correlation between the Moessbauer parameters and the decay temperatures T{sub c} of the metastable states are found. In a very thin surface layer strong color change, which remains stable at room temperature, is detected. A quadrupole doublet with Moessbauer parameters typical for Fe(III), low spin S=1/2 state is related to a new colored photoproduct. The photoproduct is called light-induced magnetic excited state (LIMES) and explained with a photochemical redox reaction, which changes the valence, spin, and magnetic state of 4f-3d bimetallic complexes. - Graphical abstract: Rare-earth nitroprussides are studied by Moessbauer spectroscopy. Population of metastable states in a thin surface layer, and another state which remains stable at room temperature, are detected. The latter is a photoproduct which is called light-induced magnetic excited state (LIMES) and explained with a photochemical redox reaction, which changes the valence, spin, and magnetic state of 4f-3d bimetallic complexes.

  7. Doping Dependence of Normal-State Properties in Iron-Based Oxypnictide Superconductor LaFeAsO1-y Probed by 57Fe-NMR and 75As-NMR/NQR

    NASA Astrophysics Data System (ADS)

    Mukuda, Hidekazu; Terasaki, Nobuyuki; Tamura, Nobukatsu; Kinouchi, Hiroaki; Yashima, Mitsuharu; Kitaoka, Yoshio; Miyazawa, Kiichi; Shirage, Parasharam M.; Suzuki, Shinnosuke; Miyasaka, Shigeki; Tajima, Setsuko; Kito, Hijiri; Eisaki, Hiroshi; Iyo, Akira

    2009-08-01

    We report systematic 57Fe-NMR and 75As-NMR/NQR studies on an underdoped sample (Tc=20 K), an optimally doped sample (Tc=28 K), and an overdoped sample (Tc=22 K) of oxygen-deficient iron (Fe)-based oxypnictide superconductor LaFeAsO1-y. A microscopic phase separation between superconducting domains and magnetic domains is shown to take place in the underdoped sample, indicating a local inhomogeneity in association with the density distribution of oxygen deficiencies. As a result, 1/T1T in the normal state of the superconducting domain decreases significantly upon cooling at both the Fe and As sites regardless of the electron-doping level in LaFeAsO1-y. On the basis of this result, we claim that 1/T1T is not always enhanced by antiferromagnetic fluctuations close to an antiferromagnetic phase in the underdoped superconducting sample. This contrasts with the behavior in hole-doped Ba0.6K0.4Fe2As2 (Tc=38 K), which exhibits a significant increase in 1/T1T upon cooling. We remark that the crucial difference between the normal-state properties of LaFeAsO1-y and Ba0.6K0.4Fe2As2 originates from the fact that the relevant Fermi surface topologies are differently modified depending on whether electrons or holes are doped into the FeAs layers.

  8. Design of the MsAa-4 Moessbauer Spectrometer

    SciTech Connect

    Blachowski, A.; Ruebenbauer, K.; Zukrowski, J.; Gornicki, R.

    2008-10-28

    An entirely new Moessbauer spectrometer MsAa-4 is currently being under design and construction. New features as compared to the basic features of the previous generation MsAa-3 spectrometer could be summarized as follows. Completely digital processing of the {gamma}-ray detector signal beyond the Gaussian shape filter/amplifier is to be implemented. The spectrometer is going to be able to accommodate external multiple detector heads. Up to 128 {gamma}-ray spectra in 16384 channels of 32-bit each and up to 512 Moessbauer spectra in 4096 channels of 32-bit each could be collected simultaneously, provided the proper external multiple detector head is used. The count-rate per single detector is limited to about 10{sup 5} counts per second in total. Improved precision of the reference function from 12-bit to 16-bit is to be provided. The reference function is stored in 8192 channels per a complete cycle. Addition of the random noise to the reference corner prism of the Michelson-Morley calibration interferometer is to be introduced to avoid spurious fringes due to the phase lock-up. An integrated universal temperature controller being able to use a variety of the temperature sensors is to be interconnected properly with the spectrometer. The spectrometer is now a stand-alone network device as it is equipped with the Ethernet connection to the outside world. Fast and high precision digital oscilloscope is to be incorporated to the spectrometer as the intrinsic unit. This oscilloscope could monitor signals at various crucial points of the internal spectrometer electronics. Modular design and use of the strict standards allows easy reconfiguration for other applications than Moessbauer spectroscopy.

  9. Structure comparison between Th2Zn17-type and TbCu7-type Sm Fe intermetallic compounds and their nitrides by means of 57Fe-Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Sakai, Yoichi; Omatsuzawa, Ryo; Sakazaki, Iwao; Suzuki, Sayaka; Hashino, Hayato; Saito, Takanobu; Iriyama, Takahiko

    2005-11-01

    Samarium iron intermetallic compounds were prepared by a melt spinning method with low and high wheel speeds, which resulted in a Th2Zn17-type and a TbCu7-type structure, respectively. Structure comparison between these types was investigated for Sm Fe intermetallic compounds and their nitrides by 57Fe-Mössbauer spectroscopy.

  10. Magnetic hysteresis properties and 57Fe Mössbauer spectroscopy of iron and stony-iron meteorites: Implications for mineralogy and thermal history

    NASA Astrophysics Data System (ADS)

    Dos Santos, E.; Gattacceca, J.; Rochette, P.; Scorzelli, R. B.; Fillion, G.

    2015-05-01

    Since the solid matter in our solar system began to assemble 4.57 billion years ago, meteorites have recorded a large range of processes, including metamorphism, melting, irradiation and hypervelocity impacts. These processes as well as solar system magnetic fields can be accessed through the investigation of magnetic properties of meteorites. In this work, we present magnetic hysteresis properties, isothermal remanent magnetization acquisition curves and 57Fe Mössbauer spectra for nineteen iron and eleven stony-iron meteorites. These data will be the background for a discussion about the thermal and shock history of these meteorites. Although Mössbauer spectroscopy and hysteresis measurements are not able to provide cooling rates like the conventional metallographic method does, we show that the combination of the ordering degree of taenite phase measured by Mössbauer spectroscopy and hysteresis properties are useful for constraining the thermal and shock history of meteorites. In particular, strong shock and the associated thermal event that result in disordering of tetrataenite can be easily identified.

  11. High field magnetic transitions in the mixed holmium-yttrium iron garnet Ho(0.43)Y(2.57)Fe(5)O(12).

    PubMed

    Bouguerra, A; Khène, S; de Brion, S; Chouteau, G; Fillion, G

    2005-01-12

    High static magnetic field magnetization measurements have been performed up to 23 T on Ho(0.43)Y(2.57)Fe(5)O(12) single crystals at helium temperature (T = 4.2 K) with fields applied along the three main cubic axes: [Formula: see text], [Formula: see text] and [Formula: see text]. The change from the spontaneous ferrimagnetic structure in zero magnetic field to the fully ferromagnetic one in high field takes place through several intermediate phases separated by transitions with step-like magnetization behaviour, but without any observed hysteresis. Using the effective spin Hamiltonian approximation, we show that the general features of these transitions can be accounted for by a large magnetocristalline anisotropy of the Ho(3+) moments of the uniaxial type along the local z axis of each rare-earth site. The model is in better agreement with the experiments than its Ising limit, widely used before, but is still unsuccessful in predicting the 'umbrella' magnetic structures found by previous neutron and NMR experiments.

  12. Transition to collapsed tetragonal phase in CaFe2As2 single crystals as seen by 57Fe Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Bud'ko, Sergey L.; Ma, Xiaoming; Tomić, Milan; Ran, Sheng; Valentí, Roser; Canfield, Paul C.

    2016-01-01

    Temperature dependent measurements of 57Fe Mössbauer spectra on CaFe2As2 single crystals in the tetragonal and collapsed tetragonal phases are reported. Clear features in the temperature dependencies of the isomer shift, relative spectra area, and quadrupole splitting are observed at the transition from the tetragonal to the collapsed tetragonal phase. From the temperature dependent isomer shift and spectral area data, an average stiffening of the phonon modes in the collapsed tetragonal phase is inferred. The quadrupole splitting increases by ˜25 % on cooling from room temperature to ˜100 K in the tetragonal phase and is only weakly temperature dependent at low temperatures in the collapsed tetragonal phase, in agreement with the anisotropic thermal expansion in this material. In order to gain microscopic insight about these measurements, we perform ab initio density functional theory calculations of the electric field gradient and the electron density of CaFe2As2 in both phases. By comparing the experimental data with the calculations we are able to fully characterize the crystal structure of the samples in the collapsed-tetragonal phase through determination of the As z coordinate. Based on the obtained temperature dependent structural data we are able to propose charge saturation of the Fe-As bond region as the mechanism behind the stabilization of the collapsed-tetragonal phase at ambient pressure.

  13. Transition to collapsed tetragonal phase in CaFe2As2 single crystals as seen by 57Fe Mössbauer spectroscopy

    DOE PAGES

    Bud'ko, Sergey L.; Ma, Xiaoming; Tomić, Milan; ...

    2016-01-21

    Temperature dependent measurements of 57Fe Mössbauer spectra on CaFe2As2 single crystals in the tetragonal and collapsed tetragonal phases are reported. Clear features in the temperature dependencies of the isomer shift, relative spectra area, and quadrupole splitting are observed at the transition from the tetragonal to the collapsed tetragonal phase. From the temperature dependent isomer shift and spectral area data, an average stiffening of the phonon modes in the collapsed tetragonal phase is inferred. The quadrupole splitting increases by ~25% on cooling from room temperature to ~100 K in the tetragonal phase and is only weakly temperature dependent at low temperaturesmore » in the collapsed tetragonal phase, in agreement with the anisotropic thermal expansion in this material. In order to gain microscopic insight about these measurements, we perform ab initio density functional theory calculations of the electric field gradient and the electron density of CaFe2As2 in both phases. By comparing the experimental data with the calculations we are able to fully characterize the crystal structure of the samples in the collapsed-tetragonal phase through determination of the As z coordinate. Furthermore, based on the obtained temperature dependent structural data we are able to propose charge saturation of the Fe-As bond region as the mechanism behind the stabilization of the collapsed-tetragonal phase at ambient pressure.« less

  14. Sensitivity of the CUORE detector to 14.4 keV solar axions emitted by the M1 nuclear transition of {sup 57}Fe

    SciTech Connect

    Li, Dawei; Creswick, Richard J.; III, Frank T. Avignone; Wang, Yuanxu E-mail: creswick.rj@sc.edu E-mail: wangyx@henu.edu.cn

    2016-02-01

    In this paper we present a calculation of the sensitivity of the CUORE detector to the monoenergetic 14.4 keV solar axions emitted by the M1 nuclear transition of {sup 57}Fe in the Sun and detected by inverse coherent Bragg-Primakoff conversion in single-crystal TeO{sub 2} bolometers. The expected counting rate is calculated using density functional theory for the electron charge density of TeO{sub 2} and realistic background and energy resolution of CUORE. Monte Carlo simulations for 5y × 741 kg=3705 kg y of exposure are analyzed using time correlation of individual events with the theoretical time-dependent counting rate. We find an expected model-independent limit on the product of the axion-photon coupling and the axion-nucleon coupling g{sub aγγ}g{sub aN}{sup eff} < 1.105 × 10{sup −16} /GeV for axion masses less than 500 eV with 95% confidence level.

  15. Time differential 57Fe Mössbauer spectrometer with unique 4π YAP:Ce 122.06 keV gamma-photon detector

    NASA Astrophysics Data System (ADS)

    Novak, Petr; Pechousek, Jiri; Prochazka, Vit; Navarik, Jakub; Kouril, Lukas; Kohout, Pavel; Vrba, Vlastimil; Machala, Libor

    2016-10-01

    This paper presents a conceptually new design of the 57Fe Time Differential Mössbauer Spectrometer (TDMS) with the gamma-photon detector optimized for registration of a radiation emitted in a maximum solid angle. A high detection efficiency of 80% in 4π region was achieved for 122.06 keV photons emitted from 57Co source. Detector parameters have been optimized for the use in the Time Differential Mössbauer Spectroscopy where the high time resolution in range of 176-200 ns is highly required. Technical concept of the TDMS is based on the virtual instrumentation technique and uses fast digital oscilloscope. Performance and detector utilization have been clarified by decreasing the Mössbauer spectral line-width of K2MgFe(CN)6 reference sample from 0.33 mm/s (integral mode) to 0.23 mm/s (time differential mode). This report also describes characterization and utilization of the detector together with additional electronic blocks and two-channel fast data-acquisition system construction.

  16. Chemostratigraphy and Fe Mineralogy of the Victoria Crater Duck Bay Section: Opportunity APXS and Moessbauer Results

    NASA Technical Reports Server (NTRS)

    Mittlefehldt, D. W.; Schroeder, C.; Gellert, R.; Klingelhoefer, G.; Jolliff, B. L.; Morris, R. V.

    2008-01-01

    Meridiani Planum is a vast plain of approximately horizontally bedded sedimentary rocks composed of mixed and reworked basaltic and evaporitic sands containing secondary, diagenetic minerals [e.g., 1-5]. Because bedding planes are subparallel to topography, investigation of contiguous stratigraphy requires examining exposures in impact craters. Early in the mission (sols 130-317), Opportunity was commanded to do detailed study of exposed outcrops in Endurance crater, including the contiguous Karatepe section at the point of ingress. Just over 1000 sols later and roughly 7 km to the south, the rover is being commanded to do a similar study of the Duck Bay section of Victoria crater. Here we report on the preliminary results from the Alpha Particle X-ray Spectrometer (APXS) and Moessbauer instruments.

  17. Redox condition of the late Neoproterozoic pelagic deep ocean: 57Fe Mössbauer analyses of pelagic mudstones in the Ediacaran accretionary complex, Wales, UK

    NASA Astrophysics Data System (ADS)

    Sato, Tomohiko; Sawaki, Yusuke; Asanuma, Hisashi; Fujisaki, Wataru; Okada, Yoshihiro; Maruyama, Shigenori; Isozaki, Yukio; Shozugawa, Katsumi; Matsuo, Motoyuki; Windley, Brian F.

    2015-11-01

    We report geological and geochemical analysis of Neoproterozoic pelagic deep-sea mudstones in an accretionary complex in Lleyn, Wales, UK. Ocean plate stratigraphy at Porth Felen, NW Lleyn, consists of mid-ocean ridge basalt (> 4 m), bedded dolostone (2 m), black mudstone (5 m), hemipelagic siliceous mudstone (1 m,) and turbiditic sandstone (15 m), in ascending order. The absence of terrigenous clastics confirms that the black and siliceous mudstone was deposited in a pelagic deep-sea. Based on the youngest U-Pb age (564 Ma) of detrital zircons separated from overlying sandstone, the deep-sea black mudstone was deposited in the late Ediacaran. The 5 m-thick black mudstone contains the following distinctive lithologies: (i) black mudstone with thin pyritic layers (0.8 m), (ii) alternation of black mudstone and gray/dark gray siliceous mudstone (2.4 m), (iii) thinly-laminated dark gray shale (1 m), and (iv) black mudstone with thin pyritic layers (1 m). 57Fe Mössbauer spectroscopy confirms that these black mudstones contain pyrite without hematite. In contrast, red bedded claystones (no younger than 542 Ma) in the neighboring Braich section contain hematite as their main iron mineral. These deep-sea mudstones in the Lleyn Peninsula record a change of redox condition on the pelagic deep-sea floor during the Ediacaran. The black mudstone at Porth Felen shows that deep-sea anoxia existed in the late Ediacaran. The eventual change from a reducing to an oxidizing deep-sea environment likely occurred in the late Ediacaran (ca. 564-542 Ma).

  18. Moessbauer Spectroscopy of Soils and Rocks at Gusev Crater and Meridiani Planum

    NASA Technical Reports Server (NTRS)

    Klingelhoefer, G.; Morris, R. V.; Bernhardt, B.; Schroeder, C.; Rodionov, D.; deSouza, P. A., Jr.; Yen, A.; Renz, F.; Wdowiak, T.; Squyres, S.

    2004-01-01

    For the first time in history a Moessbauer spectrometer was placed on the surface of another planet. The miniaturized Moessbauer spectrometer MIMOS II is part of the Athena payload of NASA's twin Mars Exploration Rovers (MER) Spirit,and Opportunity. It determines the Fe-bearing mineralogy of Martian soils and rocks at the Rovers respective landing sites, Gusev crater and Meridiani Planum. First results of soil and rock measurements at both landing sites confirm a generally basaltic composition of Martian surface materials.

  19. Moessbauer spectroscopy and scanning electron microscopy of the Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Brown, Christopher L.; Oliver, Frederick W.; Hammond, Ernest C., Jr.

    1989-01-01

    Meteorites provide a wealth of information about the solar system's formation, since they have similar building blocks as the Earth's crust but have been virtually unaltered since their formation. Some stony meteorites contain minerals and silicate inclusions, called chondrules, in the matrix. Utilizing Moessbauer spectroscopy, we identified minerals in the Murchison meteorite, a carbonaceous chondritic meteorite, by the gamma ray resonance lines observed. Absorption patterns of the spectra were found due to the minerals olivine and phyllosilicate. We used a scanning electron microscope to describe the structure of the chondrules in the Murchison meteorite. The chondrules were found to be deformed due to weathering of the meteorite. Diameters varied in size from 0.2 to 0.5 mm. Further enhancement of the microscopic imagery using a digital image processor was used to describe the physical characteristics of the inclusions.

  20. Extraterrestrial Moessbauer Spectroscopy: More than Three Years of Mars Exploration and Developments for Future Missions

    NASA Technical Reports Server (NTRS)

    Schroeder, Christian; Klingelhoefer, Goestar; Morris, Richard V.; Rodionov, Daniel S.; Fleischer, Iris; Blumers, Mathias

    2007-01-01

    The NASA Mars Exploration Rovers (MER), Spirit and Opportunity, landed on the Red Planet in January 2004. Both rovers are equipped with a miniaturized Moessbauer spectrometer MIMOS II. Designed for a three months mission, both rovers and both Moessbauer instruments are still working after more than three years of exploring the Martian surface. At the beginning of the mission, with a landed intensity of the Moessbauer source of 150 mCi, a 30 minute touch and go measurement produced scientifically valuable data while a good quality Moessbauer spectrum was obtained after approximately eight hours. Now, after about five halflives of the sources have passed, Moessbauer integrations are routinely planned to last approx.48 hours. Because of this and other age-related hardware degradations of the two rover systems, measurements now occur less frequently, but are still of outstanding quality and scientific importance. Summarizing important Moessbauer results, Spirit has traversed the plains from her landing site in Gusev crater and is now, for the greater part of the mission, investigating the stratigraphically older Columbia Hills. Olivine in rocks and soils in the plains suggests that physical rather than chemical processes are currently active.

  1. Anomalous Moessbauer Fraction in Superparamagnetic Systems.

    NASA Astrophysics Data System (ADS)

    Mohie-Eldin, Mohie-Eldin Yehia

    The biological molecule ferritin and its proven synthetic counterpart polysaccharide iron complex (P.I.C.) have been shown to contain small (<100 ^circ in diameter) antiferromagnetic cores at their centers. Mossbauer studies of these molecules have revealed an anomalous drop in the Mossbauer fraction (f-factor) as the temperature rises above 30^ circK for mammalian ferritin and 60 ^circK for P.I.C. Above the blocking temperature, superparamagnetic relaxation results in the disappearance of hyperfine splitting. This thesis investigates and attempts to resolve this Lamb-Mossbauer f-Factor anomaly in these superparamagnetically relaxing systems. Chapter I deals with a basic review of theories of Mossbauer spectroscopy and superparamagnetism. The analogies in the composition of the two molecules is examined in Chapter II. The long range order technique of magnetization measurements is used in Chapter III to compare magnetic properties of both molecules and to verify the suggestion that the P.I.C. molecule is a good "biomimic" to ferritin based on the identification of ferrihydrite as the major mineral in both, by short range probing techniques such as X-ray diffraction. The anomaly is confirmed in P.I.C.'s Mossbauer spectra in Chapter IV. Different absorbers are used to experimentally investigate the absorber thickness effect on the Mossbauer spectra. The anomaly persists for thin absorbers. Also in Chapter V, data that is treated with FFT procedures to eliminate the thickness effect still exhibit this anomaly. We then investigated the effect of superparamagnetic relaxation on the f-factor. In Chapter VI, spin-lattice relaxation was excluded based upon a calculation of the rate of energy transfer from the spin system to the lattice. We introduce a theory in Chapter VII based on the following process as a plausible explanation of the anomaly: Superparamagnetic relaxation brings about a dynamical displacement of the Mossbauer nucleus through magnetostriction. These

  2. Strong-Coupling Spin-Singlet Superconductivity with Multiple Full Gaps in Hole-Doped Ba0.6K0.4Fe2As2 Probed by 57Fe-NMR

    NASA Astrophysics Data System (ADS)

    Yashima, Mitsuharu; Nishimura, Hideaki; Mukuda, Hidekazu; Kitaoka, Yoshio; Miyazawa, Kiichi; Shirage, Parasharam M.; Kihou, Kunihiro; Kito, Hijiri; Eisaki, Hiroshi; Iyo, Akira

    2009-10-01

    We present 57Fe-NMR measurements of the novel normal and superconducting-state characteristics of the iron-arsenide superconductor Ba0.6K0.4Fe2As2 (Tc = 38 K). In the normal state, the measured Knight shift and nuclear spin-lattice relaxation rate (1/T1) demonstrate the development of wave-number (q)-dependent spin fluctuations, except at q = 0, which may originate from the nesting across the disconnected Fermi surfaces. In the superconducting state, the spin component in the 57Fe-Knight shift decreases to almost zero at low temperatures, evidencing a spin-singlet superconducting state. The 57Fe-1/T1 results are totally consistent with a s±-wave model with multiple full gaps in the strong coupling regime. We demonstrate that the respective 1/T1 data for Ba0.6K0.4Fe2As2 and LaFeAsO0.7, which seemingly follow a T5- and a T3-like behaviors below Tc, are consistently explained in terms of this model only by changing the size of the superconducting gap.

  3. Iron Moessbauer spectroscopy: Superparamagnetism in hydrothermal vents and the search for evidence of past life on Mars

    NASA Technical Reports Server (NTRS)

    Agresti, David G.; Wdowiak, Thomas J.

    1992-01-01

    In view of the demonstrated value of Iron Moessbauer Spectroscopy (FeMS) in the study of extraterrestrial iron and the fact that, after silicon and oxygen, iron is the most abundant element on the surface of Mars, we proposed, and have under development, a backscatter Moessbauer spectrometer with x ray fluorescence capability (BaMS/XRF) for use on Mars as a geophysical prospecting instrument. Specifically, we have proposed BaMS/XRF as part of the geochemistry instrumentation on NASA's Mars Environment Survey (MESUR) mission. BaMS/XRF will have applications in: (1) the study of past environments through the examination of sedimentary material; (2) the study of the contemporary Martian environment; and (3) the study of iron-containing minerals of possible biogenic origin. Development of a reference library from a geophysical point of view for putative Martian surface materials at appropriate temperatures is now underway. We carried out preliminary optical reflectance and FeMS measurements on mineral products (iron oxyhydroxides) of deep-sea hydrothermal activity. Various aspects of this investigation are presented.

  4. Iron Moessbauer spectroscopy: Superparamagnetism in hydrothermal vents and the search for evidence of past life on Mars

    NASA Technical Reports Server (NTRS)

    Agresti, David G.; Wdowiak, Thomas J.

    1992-01-01

    In view of the demonstrated value of Iron Moessbauer Spectroscopy (FeMS) in the study of extraterrestrial iron and the fact that, after silicon and oxygen, iron is the most abundant element on the surface of Mars, we proposed, and have under development, a backscatter Moessbauer spectrometer with x ray fluorescence capability (BaMS/XRF) for use on Mars as a geophysical prospecting instrument. Specifically, we have proposed BaMS/XRF as part of the geochemistry instrumentation on NASA's Mars Environment Survey (MESUR) mission. BaMS/XRF will have applications in: (1) the study of past environments through the examination of sedimentary material; (2) the study of the contemporary Martian environment; and (3) the study of iron-containing minerals of possible biogenic origin. Development of a reference library from a geophysical point of view for putative Martian surface materials at appropriate temperatures is now underway. We carried out preliminary optical reflectance and FeMS measurements on mineral products (iron oxyhydroxides) of deep-sea hydrothermal activity. Various aspects of this investigation are presented.

  5. Noncollinear Fe spin structure in (Sm-Co)/Fe exchange-spring bilayers: Layer-resolved 57Fe Mössbauer spectroscopy and electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Uzdin, V. M.; Vega, A.; Khrenov, A.; Keune, W.; Kuncser, V. E.; Jiang, J. S.; Bader, S. D.

    2012-01-01

    Magnetization reversal in nanoscale (Sm-Co)/Fe (hard/soft) bilayer exchange-spring magnets with in-plane uniaxial magnetic anisotropy was investigated by magnetometry, conversion-electron Mössbauer spectroscopy (CEMS) and atomistic Fe spin-structure calculations. Magnetization loops along the easy direction exhibit signatures typical of exchange-spring magnets. In-field CEMS at inclined γ-ray incidence onto thin (2 nm) 57Fe probe layers embedded at various depths in the 20-nm-thick natural (soft) Fe layer provides depth-dependent information (via the line-intensity ratio R23 as a function of the applied field H) about the in-plane rotation of Fe spins. A minimum in the R23-vs-H dependence at (Hmin, Rmin) determines the field where Fe magnetic moments roughly adopt an average perpendicular orientation during their reversal from positive to negative easy-axis orientation. A monotonic decrease of Hmin with distance from the hard/soft interface is observed. Rotation of Fe spins takes place even in the interface region in applied fields far below the field of irreversible switching, Hirr, of the hard phase. Formation of an Fe-Co alloy is detected in the interface region. For comparison, the noncollinear Fe spin structure during reversal and the resulting R23 ratio were obtained by electronic-structure calculations based on a quantum-mechanical Hamiltonian for itinerant electrons. The coupling at the hard/soft interface is described by the uniaxial exchange-anisotropy field, hint, as a parameter. Our calculated R23 ratios as a function of the (reduced) applied field h exhibit similar features as observed in the experiment, in particular a minimum at (hmin, Rmin). Rmin is found to increase with hint, thus providing a measure of the interface coupling. Evidence is provided for the existence of fluctuations of the interface coupling. The calculations also show that the Fe spin spiral formed during reversal is highly inhomogeneous. In general, our simulation of the Fe spin

  6. Moessbauer effect measurement in single crystal iron subjected to cyclic stress

    NASA Technical Reports Server (NTRS)

    Singh, J. J.

    1976-01-01

    Backscattered Moessbauer spectra were recorded at different fatigue levels in cyclically fatigued high-purity single-crystal iron specimens in the form of rectangular strips with appropriate concentrators in the midplane. The Moessbauer spectra were submitted to a least-squares analysis to determine the isomer shift, quadrupole shift, hyperfine field, and peak spectral widths in each spectrum. It is shown that the quadrupole shift and the isomer shift changed little with fatigue, whereas the effective internal field and the associate line widths exhibit significant variation as a function of fatigue level. It is concluded that the impurity concentration builds up slowly with increasing fatigue level in the region of stress concentration. Since there is a direct correlation between crack initiation and defect concentration level, it is expected that Moessbauer measurements in the test specimen can provide a means of monitoring the impurity buildup presumed to be the eventual cause of fatigue crack initiation and failure.

  7. Moessbauer spectroscopy evidence of a spinodal mechanism for the thermal decomposition of fcc FeCu

    SciTech Connect

    Crespo, P. |; Barro, M.J.; Hernando, A.; Escorial, A.G.; Menendez, N.; Tornero, J.D.; Barandiaran, J.M.

    1998-07-24

    Moessbauer spectroscopy shows the existence of compositional fluctuations, where different Fe environments coexist, during decomposition upon heat treatment of metastable f.c.c. FeCu solid solution. The presence of isolated Fe atoms in the Cu matrix, f.c.c. Fe{sub rich}Cu, f.c.c. FeCu{sub rich} and b.c.c. Fe has been detected in early decomposition stages. At later decomposition stages, low temperature Moessbauer spectroscopy indicates the presence of a broad distribution of Curie temperatures, coexisting with isolated Fe atoms in the Cu matrix, f.c.c. Fe and b.c.c. Fe.

  8. Moessbauer spectroscopy of Mg(0.9)Fe(0.1)SiO3 perovskite

    NASA Technical Reports Server (NTRS)

    Jeanloz, Raymond; O'Neill, Bridget; Pasternak, Moshe P.; Taylor, R. D.; Bohlen, Steven R.

    1992-01-01

    Ambient pressure Moessbauer spectra of Mg(0.9)Fe-57(0.1)SiO3 perovskite synthesized at pressure-temperature conditions of about 50 GPa and 1700 K show that the iron is entirely high-spin Fe(2+) and appears to be primarily located in the octahedral site within the crystal structure. We observe broad Moessbauer lines, suggesting a distribution of electric-field gradients caused by disorder associated with the Fe ions. Also, the perovskite exhibits magnetic ordering at temperatures lower than 5 K, implying that there is a magnetic contribution to the absolute ('third-law') entropy of this phase.

  9. Cronstedtite and iron sulfide mineralogy of CM-type carbonaceous chondrites from cryogenic Moessbauer spectra

    NASA Technical Reports Server (NTRS)

    Fisher, Duncan S.; Burns, Roger G.

    1993-01-01

    Determinations of oxidation states and the crystal chemistry of iron-bearing minerals in CM meteorites by Moessbauer spectroscopy are complicated by thermally-induced electron hopping in cronstedtite and by ill-defined contributions from the hydrous iron sulphide phase believed to be tochilinite. Moessbauer spectral measurements at 30 K of several cronstedtite and tochilinite specimens have enabled modal proportions of these minerals, as well as Fe(3+)/Fe(2+) ratios, to be determined quantitatively for a suite of CM-type carbonaceous chondrites that included Murchison, Murray, Cold Bokkeveld, ALH 83100, and LEW 90500.

  10. The big and little of fifty years of Moessbauer spectroscopy at Argonne.

    SciTech Connect

    Westfall, C.

    2005-09-20

    Using radioactive materials obtained by chance, a turntable employing gears from Heidelberg's mechanical toy shops, and other minimal equipment available in post World War II Germany, in 1959 Rudolf Moessbauer confirmed his suspicion that his graduate research had yielded ground-breaking results. He published his conclusion: an atomic nucleus in a crystal undergoes negligible recoil when it emits a low energy gamma ray and provides the entire energy to the gamma ray. In the beginning Moessbauer's news might have been dismissed. As Argonne nuclear physicist Gilbert Perlow noted: ''Everybody knew that nuclei were supposed to recoil when emitting gamma rays--people made those measurements every day''. If any such effect existed, why had no one noticed it before? The notion that some nuclei would not recoil was ''completely crazy'', in the words of the eminent University of Illinois condensed matter physicist Frederich Seitz. Intrigued, however, nuclear physicists as well as condensed matter (or solid state) physicists in various locations--but particularly at the Atomic Energy Research Establishment at Harwell in Britain and at Argonne and Los Alamos in the U.S.--found themselves pondering the Moessbauer spectra with its nuclear and solid state properties starting in late 1959. After an exciting year during which Moessbauer's ideas were confirmed and extended, the physics community concluded that Moessbauer was right. Moessbauer won the Nobel Prize for his work in 1961. In the 1960s and 1970s Argonne physicists produced an increasingly clear picture of the properties of matter using the spectroscopy ushered in by Moessbauer. The scale of this traditional Moessbauer spectroscopy, which required a radioactive source and other simple equipment, began quite modestly by Argonne standards. For example Argonne hosted traditional Moessbauer spectroscopy research using mostly existing equipment in the early days and equipment that cost $100,000 by the 1970s alongside work at

  11. Moessbauer spectroscopy of Mg(0.9)Fe(0.1)SiO3 perovskite

    NASA Technical Reports Server (NTRS)

    Jeanloz, Raymond; O'Neill, Bridget; Pasternak, Moshe P.; Taylor, R. D.; Bohlen, Steven R.

    1992-01-01

    Ambient pressure Moessbauer spectra of Mg(0.9)Fe-57(0.1)SiO3 perovskite synthesized at pressure-temperature conditions of about 50 GPa and 1700 K show that the iron is entirely high-spin Fe(2+) and appears to be primarily located in the octahedral site within the crystal structure. We observe broad Moessbauer lines, suggesting a distribution of electric-field gradients caused by disorder associated with the Fe ions. Also, the perovskite exhibits magnetic ordering at temperatures lower than 5 K, implying that there is a magnetic contribution to the absolute ('third-law') entropy of this phase.

  12. Moessbauer and Positron Annihilation Spectroscopy Applied to WWER-1000 RPV Steels

    SciTech Connect

    Slugen, V.; Lipka, J.; Zeman, A.; Debarberis, L.

    2005-04-26

    Moessbauer spectroscopy (MS) and Positron annihilation spectroscopy (PAS) were applied in the evaluation of the microstructure parameters and degradation processes of nuclear reactor pressure vessel (RPV) steel surveillance specimens. Study was oriented to the material investigation of Russian WWER-1000 steels (15Kh2MNFAA and 12Kh2N2MAA) with higher Ni content (1.26 wt.% in base metal and 1.7 wt.% in weld). For comparison, the WWER-440 weld metal (Sv10KhMFT) without Ni was measured too. Specimens were studied in as received form, after irradiation in LVR-15 experimental reactor to the neutron fluence F(E>0.5 MeV) = 1.47x1024 m-2s-1 and after annealing process in vacuum at 475 deg. C/2h. Changes due to different chemical composition and due to irradiation were registered using MS. Post-irradiation thermal treatment and annealing of defects was well detected by different PAS techniques. Results confirm the hypothesis that Ni affects size (decrease) and distribution (more homogeneous) of the Cu- and P-rich clusters and MxCx carbides.

  13. An Overview of Moessbauer Mineralogy at Gusev Crater, Mars

    NASA Technical Reports Server (NTRS)

    Klingelhoefer, G.; Schroeder, C.; Rodionov, D.; Yen, A.

    2006-01-01

    The Mars Exploration Rover (MER) Spirit landed on the plains of Gusev Crater on 4 January 2004 [1]. The scientific objective of the Moessbauer (MB) spectrometer on Spirit is to provide quantitative information about the distribution of Fe among its oxidation and coordination states, identification of Fe-bearing phases, and relative distribution of Fe among those phases. The speciation and distribution of Fe in Martian rock and soil constrains the primary rock types, redox conditions under which primary minerals crystallized, the extent of alteration and weathering, the type of alteration and weathering products, and the processes and environmental conditions for alteration and weathering.We discuss the Fe-bearing phases detected by Spirit s MB instrument during its first 540 sols of exploration [2,3]. Spirit roved eastward across the plains from its landing site to the Columbia Hills during the first approx.150 sols. Rocks are unweathered to weakly weathered olivine basalt, with olivine, pyroxene (Ol > Px), magnetite (Mt), and minor hematite (Hm) and nanophase ferric oxide (npOx) as their primary Fe-bearing minerals. Soils are generally similar basaltic materials, except that the proportion of npOx is much higher (up to approx.40%). NpOx is an oct-Fe3+ alteration product whose concentration is highest in fine-grained soils and lowest in rock interiors exposed by grinding with the Rock Abrasion Tool (RAT). Spirit explored the lower slopes of the Columbia Hills (West Spur) during sols approx.150-320. West Spur rocks are highly altered, even for interior surfaces exposed by grinding (Fe3+/FeT approx.0.56-0.84). High concentrations of npOx, Hm, and Mt are present. One rock (Clovis) contains significant quantities of goethite (alpha-FeOOH; approx.40% of total Fe). The detection of goethite is very significant because it is a mineralogical marker for aqueous alteration.

  14. Investigation of the Moessbauer Spectrum Quality as a Dependence on the Frequency of the Velocity Signal

    SciTech Connect

    Pechousek, J.

    2010-07-13

    This paper is focused on a quality characterizing the Moessbauer spectra measured for various frequencies of the velocity signal. Standard electromechanical double-loudspeaker drive and digital PID velocity controller were used for calibration spectra measurement in the frequency interval from 4 up to 100 Hz. Several parameters were evaluated for recommendation of the suitable velocity signal frequency.

  15. Moessbauer medium with a hidden nuclear population inversion and negative absorption of gamma quanta

    SciTech Connect

    Rivlin, Lev A

    2011-06-30

    We consider physical foundations of an eventual experiment aimed at observing stimulated gamma-photon emission of long-lived Moessbauer isomers through selective frequency modulation of gamma-resonances establishing hidden population inversion without exceeding the number of excited nuclei over unexcited ones and without additional pumping. The examples of suitable nuclei and numerical estimates of the parameters are presented. (active media)

  16. Fe-doped ZnO nanoparticles: the oxidation number and local charge on iron, studied by 57Fe Mößbauer spectroscopy and DFT calculations.

    PubMed

    Xiao, Jianping; Kuc, Agnieszka; Pokhrel, Suman; Mädler, Lutz; Pöttgen, Rainer; Winter, Florian; Frauenheim, Thomas; Heine, Thomas

    2013-03-04

    Iron bru: Fe-doped ZnO may contain Fe(2+) and Fe(3+) species. Whilst Mößbauer spectroscopy can distinguish these sites in pure oxides FeO and Fe(2)O(3), it gives very similar shifts for Fe-doped phases. This result is rationalized by electron redistribution from the dopant site to the crystal matrix. Mößbauer shifts correlate with the local charge on the Fe sites and different dopant sites can be identified by the Mößbauer quadrupole splitting (see figure).

  17. An 57Fe Mössbauer spectral study of Gd 2Fe 17H x (for x=0, 3, and 5) and Sm 2Fe 17D 5

    NASA Astrophysics Data System (ADS)

    Hautot, Dimitri; Long, Gary J.; Grandjean, F.; Isnard, O.; Fruchart, D.

    1999-07-01

    The Mössbauer spectra of Gd 2Fe 17H x (for x=0, 3, and 5) and Sm 2Fe 17D 5 have been measured between 85 and 295 K and have been analysed with a model which takes into account the basal orientation of the iron magnetic moments, the near-neighbor enviornment of the four crystallographically inequivalent iron sites, and the structural changes occuring upon hydrogen or deuterium insertion. The temperature dependences of the individual iron site isomer shifts and hyperfine fields follow the expected second-order Doppler shift and Brillouin law behavior, respectively, and provide support for the adequacy of the fitting model. The increases in the isomer shifts upon going from R 2Fe 17, to R 2Fe 17H 3, to R 2Fe 17H 5, and finally to R 2Fe 17N 3, where R is a rare-earth atom, correlate well with the observed increases in the unit-cell volume and the iron Wigner-Seitz cell volumes upon hydrogen and nitrogen insertion. The 85 K weighted average hyperfine field in R 2Fe 17 and R 2Fe 17H 3 is at a maximum for the gadolinium compounds in agreement with their higher Curie temperatures. Pr 2Fe 17H 3 and Sm 2Fe 17N 3, which both exhibit axial magnetization, show large 85 K weighted average hyperfine fields than the remaining R 2Fe 17H 3 and R 2Fe 17N 3 compounds, respectively. Finally, the differences in the 18h iron site environment, due to the insertion of the fourth and fifth hydrogen atoms into R 2Fe 17H 5, where R is Nd, Sm, and Gd, are not observed in the Mössbauer spectra, and hence the hydrogen atoms on the 18g tetrahedral interstitial sites must be rapidly moving on the Mössbauer timescale. The magnetization curves of Sm 2Fe 17 and Sm 2Fe 17D 5 have been measured at 5 and 300 K. The increase in the saturation magnetization upon deuterium insertion is well explained by the increase in the Curie temperature and correlates very well with the increase in the 85 K weighted average hyperfine field.

  18. Effects of Al substitution and thermal annealing on magnetoelectric Ba0.5Sr1.5Zn2Fe12O22 investigated by the enhancement factor of 57Fe nuclear magnetic resonance.

    PubMed

    Kwon, Sangil; Kang, Byeongki; Kim, Changsoo; Jo, Euna; Lee, Soonchil; Chai, Yi Sheng; Chun, Sae Hwan; Kim, Kee Hoon

    2014-04-09

    The magnetoelectric properties of hexaferrite Ba0.5Sr1.5Zn2Fe12O22 are significantly improved by Al substitution and thermal annealing. Measuring the enhancement factor of 57Fe NMR, we found direct microscopic evidence that the magnetic moments of the L and S blocks are rotated by a magnetic field in such a way as to increase the net magnetic moment of a magnetic unit, even after the field is removed. Al substitution makes magnetoelectric property arise easily by suppressing the easy-plane anisotropy. The effect of thermal annealing is to stabilize the multiferroic state by reducing the number of pinning sites and the electron spin fluctuation. The transverse conic structure gradually changes to the alternating longitudinal conic structure where spins fluctuate more severely.

  19. Hematite at Meridiani Planum and Gusev Crater as identified by the Moessbauer Spectrometer MIMOS II

    NASA Technical Reports Server (NTRS)

    Klingelhoefer, G.; Morris, R. V.; Rodionov, D.; Schroeder, C.; de Souza, P. A.; Yen, A.; Renz, F.; Wdowiak, T.

    2006-01-01

    The Moessbauer (MB) spectrometers on the MER rovers Opportunity and Spirit, which landed on Mars in January 2004, have identified the iron-containing mineral hematite (a-Fe2O3) at both landing sites. On Earth, hematite can occur either by itself or with other iron oxides as massive deposits, in veins , and as particles dispersed through a silicate or other matrix material. Hematite particle size can range from nanophase (superparamagnetic) to multidomain and particle shape ranges from equant to acicular to platy. Fine-grained hematite is red in color and is a pigmenting agent. Coarse-grained hematite can be spectrally neutral (gray) at visible wavelengths. Substitutional impurities, particularly Al, are common in hematite. Chemically pure, coarse-grained, and well-crystalline hematite has a magnetic transition (the Morin transition) at 260 K. Moessbauer spectra, recorded as a function of temperature, provide a way to characterize Martian hematite with respect to some of the physical and chemical characteristics. At Meridiani Planum besides the iron-sulfate mineral jarosite also the Fe-oxide hematite has been identified by the Moessbauer spectrometer, mainly in three distinct types of reservoir: - outcrop matrix material dominated by the mineral jarosite in the MB spectrum, certain basaltic soils, and mm-sized spherules dubbed blueberries. Moessbauer spectra of each reservoir yield a distinct set of hyperfine parameters for hematite, suggesting different degrees of crystallinity and particle size. The hematite found by MB instrument MIMOS II in the outcrop material shows the Morin transition at relatively high temperatures (ca. 250 K) which is an indication of pure and well-crystallized hematite. The source of the hematite in the Blueberries as identified by Moessbauer spectroscopy, and also by MiniTES, is not known. These spherules, covering nearly the whole landing site area (Eagle crater, plains, Endurance crater), may be concretions formed in the outcrop

  20. Hematite at Meridiani Planum and Gusev Crater as identified by the Moessbauer Spectrometer MIMOS II

    NASA Technical Reports Server (NTRS)

    Klingelhoefer, G.; Morris, R. V.; Rodionov, D.; Schroeder, C.; de Souza, P. A.; Yen, A.; Renz, F.; Wdowiak, T.

    2006-01-01

    The Moessbauer (MB) spectrometers on the MER rovers Opportunity and Spirit, which landed on Mars in January 2004, have identified the iron-containing mineral hematite (a-Fe2O3) at both landing sites. On Earth, hematite can occur either by itself or with other iron oxides as massive deposits, in veins , and as particles dispersed through a silicate or other matrix material. Hematite particle size can range from nanophase (superparamagnetic) to multidomain and particle shape ranges from equant to acicular to platy. Fine-grained hematite is red in color and is a pigmenting agent. Coarse-grained hematite can be spectrally neutral (gray) at visible wavelengths. Substitutional impurities, particularly Al, are common in hematite. Chemically pure, coarse-grained, and well-crystalline hematite has a magnetic transition (the Morin transition) at 260 K. Moessbauer spectra, recorded as a function of temperature, provide a way to characterize Martian hematite with respect to some of the physical and chemical characteristics. At Meridiani Planum besides the iron-sulfate mineral jarosite also the Fe-oxide hematite has been identified by the Moessbauer spectrometer, mainly in three distinct types of reservoir: - outcrop matrix material dominated by the mineral jarosite in the MB spectrum, certain basaltic soils, and mm-sized spherules dubbed blueberries. Moessbauer spectra of each reservoir yield a distinct set of hyperfine parameters for hematite, suggesting different degrees of crystallinity and particle size. The hematite found by MB instrument MIMOS II in the outcrop material shows the Morin transition at relatively high temperatures (ca. 250 K) which is an indication of pure and well-crystallized hematite. The source of the hematite in the Blueberries as identified by Moessbauer spectroscopy, and also by MiniTES, is not known. These spherules, covering nearly the whole landing site area (Eagle crater, plains, Endurance crater), may be concretions formed in the outcrop

  1. Scrutinizing Al-like 10+51V, 11+53Cr, 12+55Mn, 13+57Fe, 14+59Co, 15+61Ni, and 16+63Cu 1ions for atomic clocks with uncertainties below the 10-19 level

    NASA Astrophysics Data System (ADS)

    Yu, Yan-mei; Sahoo, B. K.

    2016-12-01

    We investigate the transition between the fine structure levels of the ground state, 3 p 2P1 /2→3 p 2P3 /2 , of the highly charged Al-like 10+51V, 11+53Cr, 12+55Mn, 13+57Fe, 14+59Co, 15+61Ni, and 16+63Cu ions for frequency standards. To comprehend them as prospective atomic clocks, we determine their transition wavelengths, quality factors, and various plausible systematics during the measurements. Since most of these ions have nuclear spin I =3 /2 , uncertainties due to dominant quadrupole shifts can be evaded in the F =0 hyperfine level of the 3 p 2P3 /2 state. Other dominant systematics such as quadratic Stark and black-body radiation shifts have been evaluated precisely demonstrating the feasibility of achieving high accuracy, below 10-19 fractional uncertainty, atomic clocks using the above transitions. Moreover, relativistic sensitivity coefficients are determined to find out the aptness of these proposed clocks to investigate possible temporal variation of the fine structure constant. To carry out these analysis, a relativistic coupled-cluster method considering Dirac-Coulomb-Breit Hamiltonian along with lower-order quantum electrodynamics interactions is employed and many spectroscopic properties are evaluated. These properties are also of immense interest for astrophysical studies.

  2. 57Fe Mössbauer spectroscopy investigations of iron oxidation states in the Harmattan dust nutrient contribution to West African soils

    NASA Astrophysics Data System (ADS)

    Adetunji, Jacob

    2014-12-01

    A variety of investigations have been carried out on Harmattan dust over many decades demonstrating the continuing importance of the Harmattan dust phenomenon. The investigations have included elemental enrichment factors, mineralogical nutrient input through dust deposition on the soil, meteorological studies, etc. Harmattan dust is important, not only for its impact on radio communication and low visibility in the shipping lanes over the Atlantic, but also on the livelihood and health of people living in countries over which the dust-laden Harmattan wind blows. However, so far, the aspect of nutrient mineral deposition on the soil has not been thoroughly investigated and requires attention, since the majority of people living in West Africa rely heavily on agriculture. It is therefore relevant to know the useful nutrients in the Harmattan dust deposited on soils of the region. This study is therefore aimed at determining the ferric-ferrous ratio of the iron-bearing minerals contained in the Harmattan dust, so their nutritional contribution can be considered. The Mössbauer technique is a powerful tool for studying the ferric-ferrous ratio and has therefore been used, for the first time, to determine the oxidation states of iron in the dust samples. The results of the analysis show that the Harmattan dust is seriously deficient in ferrous iron, which is the more soluble Fe-ion, needed in the soil for healthy crops and plants in general.

  3. Effects of the host matrix on the 57Fe-species produced through EC-decay in 57Co-labelled tris(phenanthroline) cobalt (II) perchlorate.

    PubMed

    Endo, K; Amano, M; Sano, H

    1979-04-01

    Emission Mössbauer spectroscopic studies of 57Co-labelled [Co(phen)3]clO4)2 in host matrices [M(II)(phen)3](ClO4)2(M=Co, Fe, and Ni) indicate that the relative intensities of the anomalous species produced through the EC-decay depend on the kind of the host matrix. The largest intensity was observed with the cobalt (II) matrix, and the smallest with the iron (II) matrix. Emission spectra of 57Co-labelled [Co(2-CH3-phen)3](ClO4)2 2H2O in the matrix of [Fe(2-CH3-phen)3](ClO4)2 were also studied. The high-spin state (5T2) was predominantly observed at 4.2 K in the emission spectrum, while the low-spin state (1A1) was mainly observed in the absorption spectrum at 78 K. The results are discussed in terms of the stability of the lattice.

  4. Study on Mössbauer spectra of hemoglobin in thalassemia

    NASA Astrophysics Data System (ADS)

    Xuanhui, Guo; Nanming, Zhao; Xiufang, Zhang; Naifei, Gao; Youwen, Huang; Rongxin, Wang

    1988-02-01

    The57Fe Mössbauer spectra of erythrocytes in normal subjects and nine patients of different thalassemias were studied. Together with clinical analysis, the correlation between the components in the spectra and different types of anemias was discussed.

  5. Density Functional Calculations for Prediction of (57)Fe Mössbauer Isomer Shifts and Quadrupole Splittings in β-Diketiminate Complexes.

    PubMed

    McWilliams, Sean F; Brennan-Wydra, Emma; MacLeod, K Cory; Holland, Patrick L

    2017-06-30

    The relative ease of Mössbauer spectroscopy and of density functional theory (DFT) calculations encourages the use of Mössbauer parameters as a validation method for calculations, and the use of calculations as a double check on crystallographic structures. A number of studies have proposed correlations between the computationally determined electron density at the iron nucleus and the observed isomer shift, but deviations from these correlations in low-valent iron β-diketiminate complexes encouraged us to determine a new correlation for these compounds. The use of B3LYP/def2-TZVP in the ORCA platform provides an excellent balance of accuracy and speed. We provide here not only this new correlation and a clear guide to its use but also a systematic analysis of the limitations of this approach. We also highlight the impact of crystallographic inaccuracies, DFT model truncation, and spin states, with intent to assist experimentalists to use Mössbauer spectroscopy and calculations together.

  6. Density Functional Calculations for Prediction of 57Fe Mössbauer Isomer Shifts and Quadrupole Splittings in β-Diketiminate Complexes

    PubMed Central

    2017-01-01

    The relative ease of Mössbauer spectroscopy and of density functional theory (DFT) calculations encourages the use of Mössbauer parameters as a validation method for calculations, and the use of calculations as a double check on crystallographic structures. A number of studies have proposed correlations between the computationally determined electron density at the iron nucleus and the observed isomer shift, but deviations from these correlations in low-valent iron β-diketiminate complexes encouraged us to determine a new correlation for these compounds. The use of B3LYP/def2-TZVP in the ORCA platform provides an excellent balance of accuracy and speed. We provide here not only this new correlation and a clear guide to its use but also a systematic analysis of the limitations of this approach. We also highlight the impact of crystallographic inaccuracies, DFT model truncation, and spin states, with intent to assist experimentalists to use Mössbauer spectroscopy and calculations together. PMID:28691111

  7. Internal electron conversion of the isomeric {sup 57}Fe nucleus state with an energy of 14.4 keV excited by the radiation of the plasma of a high-power femtosecond laser pulse

    SciTech Connect

    Golovin, G V; Savel'ev-Trofimov, Andrei B; Uryupina, D S; Volkov, Roman V

    2011-03-31

    We recorded the spectrum of delayed secondary electrons ejected from the target, which was coated with a layer of iron enriched with the {sup 57}Fe isotope to 98%, under its irradiation by fluxes of broadband X-ray radiation and fast electrons from the plasma produced by a femtosecond laser pulse at an intensity of 10{sup 17} W cm{sup -2}. Maxima were identified at energies of 5.6, 7.2, and 13.6 keV in the spectrum obtained for a delay of 90 - 120 ns. The two last-listed maxima owe their origin to the internal electron conversion of the isomeric level with an energy of 14.4 keV and a lifetime of 98 ns to the K and L shells of atomic iron, respectively; the first-named level arises from a cascade K - L{sub 2}L{sub 3} Auger process. Photoexcitaion by the X-ray plasma radiation is shown to be the principal channel of the isomeric level excitation. (interaction of laser radiation with matter)

  8. In-situ 57Fe Mössbauer characterization of iron oxides in pigments of a rupestrian painting from the Serra da Capivara National Park, in Brazil, with the backscattering Mössbauer spectrometer MIMOS II

    NASA Astrophysics Data System (ADS)

    Soares Meneses Lage, Maria Conceiç ao; Duarte Cavalcante, Luis Carlos; Klingelhöfer, Göstar; Fabris, José Domingos

    2016-12-01

    It is reported the use of the miniaturized portable 57Fe Mössbauer backscattering spectrometer MIMOS II to perform in situ measurements in the archaeological site known as Toca do Boqueirão do Sítio da Pedra Furada (BPF), in Serra da Capivara National Park, in order to specifically examine shades of dark red pigments and compare their differences relatively to the light red part of the same painting. The hyperfine Mössbauer parameters reveal that the dark red area of the rupestrian painting is composed of three populations of hematite and of a small proportion of maghemite, whereas the light red are of the same painting contain hematite mixed with a small proportion of maghemite and a (super)paramagnetic Fe 3+. The Fe content in the dark red area from the rupestrian painting is of approximately twice the amount in the light red of the same prehistoric graphism. The corresponding analysis of red ochre sample collected in the excavation of these archaeological site exhibited two populations of hematite and also a small proportion of maghemite.

  9. Hematite at Meridiani Planum and Gusev Crater as identified by the Moessbauer Spectrometer MIMOS II

    NASA Astrophysics Data System (ADS)

    Klingelhoefer, G.; Morris, R. V.; Rodionov, D.; Schroeder, C.; de Souza, P. A.; Yen, A.; Renz, F.; Wdowiak, T.

    2004-12-01

    The Moessbauer (MB) spectrometers on the MER rovers Opportunity and Spirit, which landed on Mars in January 2004, have identified the iron-containing mineral hematite (a-Fe2O3) at both landing sites. On Earth, hematite can occur either by itself or with other iron oxides as massive deposits, in veins , and as particles dispersed through a silicate or other matrix material. Hematite particle size can range from nanophase (superparamagnetic) to multidomain and particle shape ranges from equant to acicular to platy. Fine-grained hematite is red in color and is a pigmenting agent. Coarse-grained hematite can be spectrally neutral (gray) at visible wavelengths. Substitutional impurities, particularly Al, are common in hematite. Chemically pure, coarse-grained, and well-crystalline hematite has a magnetic transition (the Morin transition) at ~260 K. Moessbauer spectra, recorded as a function of temperature, provide a way to characterize Martian hematite with respect to some of the physical and chemical characteristics. At Meridiani Planum besides the iron-sulfate mineral jarosite also the Fe-oxide hematite has been identified by the Moessbauer spectrometer, mainly in three distinct types of reservoir: - outcrop matrix material dominated by the mineral jarosite in the MB spectrum, certain basaltic soils, and mm-sized spherules dubbed blueberries. Moessbauer spectra of each reservoir yield a distinct set of hyperfine parameters for hematite, suggesting different degrees of crystallinity and particle size. The hematite found by MB instrument MIMOS II in the outcrop material shows the Morin transition at relatively high temperatures (ca. 250 K) which is an indication of pure and well-crystallized hematite. The source of the hematite in the `Blueberries' as identified by Moessbauer spectroscopy, and also by MiniTES, is not known. These spherules, covering nearly the whole landing site area (Eagle crater, plains, Endurance crater), may be concretions formed in the outcrop

  10. Reflectivity (visible and near IR), Moessbauer, static magnetic, and X ray diffraction properties of aluminum-substituted hematites

    NASA Technical Reports Server (NTRS)

    Morris, Richard V.; Schulze, Darrell G.; Lauer, Howard V., Jr.; Agresti, David G.; Shelfer, Tad D.

    1992-01-01

    The effect of substituting iron by aluminum in polymorphs of Fe2O3 and FeOOH on their reflectivity characteristics was investigated by comparing data on visible and NIR reflectivities and on static magnetic, XRD, and Moessbauer properties for a family of aluminum-substituted hematites alpha-(Fe,Al)2O3, with compositions where the values of the Al/(Al+Fe) ratio were up to 0.61. Samples were prepared by oxidation of magnetite, dehydroxylation of goethite, and direct precipitation. The analytical methods used for obtaining diffuse reflectivity spectra (350-2200 nm), Moessbauer spectra, and static magnetic data are those described by Morris et al. (1989).

  11. Magnetic properties and Moessbauer analyses of glass from the K-T boundary, Beloc, Haiti

    NASA Technical Reports Server (NTRS)

    Senftle, F. E.; Thorpe, A. N.; May, L.; Barkatt, A.; Adel-Hadadi, M. A.; Marbury, G. S.; Izett, G.; Sigurdsson, H.; Maurasse, F. J.-M. R.

    1993-01-01

    The experimental magnetic susceptibility, the temperature-independent component of the magnetic susceptibility, the magnetization, and the Curie constant have been measured for a number of specimens of glass from the K-T boundary found at Beloc, Haiti, and the results are compared with those of similar measurements of tektites. Because the Fe(3+)/Fe(2+) ratio is needed to calculate the magnetic parameters, Moessbauer spectroscopic measurements were also made. The data were consistent with the classification of the Beloc glasses as tektites.

  12. Combined backscatter Moessbauer spectrometer/x ray fluorescence analyzer (BaMS/XRF) for extraterrestrial surfaces

    NASA Technical Reports Server (NTRS)

    Shelfer, T. D.; Wills, E. L.; Agresti, D. G.; Pimperl, M. M.; Shen, M. H.; Morris, R. V.; Nguyen, T.

    1993-01-01

    We have designed and tested a prototype combined backscatter Moessbauer spectrometer and x-ray fluorescence analyzer (BaMS/XRF). A space qualified instrument based on this design would be suitable for in-situ use on planetary missions to the surfaces of the Moon (Artemis and lunar outpost), Mars (MESUR), asteroids, or other solid solar system objects. The BaMS/XRF instrument is designed to be capable of concurrent sample analyses for the mineralogy of iron-bearing phases and elemental composition without the need for sample preparation.

  13. Combined backscatter Moessbauer spectrometer/x ray fluorescence analyzer (BaMS/XRF) for extraterrestrial surfaces

    NASA Technical Reports Server (NTRS)

    Shelfer, T. D.; Wills, E. L.; Agresti, D. G.; Pimperl, M. M.; Shen, M. H.; Morris, R. V.; Nguyen, T.

    1993-01-01

    We have designed and tested a prototype combined backscatter Moessbauer spectrometer and x-ray fluorescence analyzer (BaMS/XRF). A space qualified instrument based on this design would be suitable for in-situ use on planetary missions to the surfaces of the Moon (Artemis and lunar outpost), Mars (MESUR), asteroids, or other solid solar system objects. The BaMS/XRF instrument is designed to be capable of concurrent sample analyses for the mineralogy of iron-bearing phases and elemental composition without the need for sample preparation.

  14. Mineralogical diversity (spectral reflectance and Moessbauer data) in compositionally similar impact melt rocks from Manicouagan Crater, Canada

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Bell, J. F., III; Golden, D. C.; Lauer, H. V., Jr.

    1993-01-01

    Meteoritic impacts under oxidizing surface conditions occur on both earth and Mars. Oxidative alteration of impact melt sheets is reported at several terrestrial impact structures including Manicouagan, West Clearwater Lake, and the Ries Basin. A number of studies have advocated that a significant fraction of Martian soil may consist of erosional products of oxidatively altered impact melt sheets. If so, the signature of the Fe-bearing mineralogies formed by the process may be present in visible and near infrared reflectivity data for the Martian surface. Of concern is what mineral assemblages form in impact melt sheets produced under oxidizing conditions and what their spectral signatures are. Spectral and Moessbauer data for 19 powder samples of impact melt rock from Manicouagan Crater are reported. Results show for naturally occurring materials that composite hematite-pyroxene bands have minima in the 910-nm region. Thus many of the anomalous Phobos-2 spectra, characterized by a shallow band minimum in the near-IR whose position varies between approximately 850 and 1000 nm, can be explained by assemblages whose endmembers (hematite and pyroxene) are accepted to be present on Mars. Furthermore, results show that a mineralogically diverse suite of rocks can be generated at essentially constant composition, which implies that variations in Martian surface mineralogy do not necessarily imply variations in chemical composition.

  15. Characterization of magnetite in silico-aluminous fly ash by SEM, TEM, XRD, magnetic susceptibility, and Moessbauer spectroscopy

    SciTech Connect

    Gomes, S.; Francois, M.; Abdelmoula, M.; Refait, P.; Pellissier, C.; Evrard, O.

    1999-11-01

    Spinel magnetite contained in a silico-aluminous fly ash (originating from la Maxe's power plant, near Metz in the east of France) issued from bituminous coal combustion has been studied by scanning and transmission electron microscopy linked with energy dispersive spectroscopy. X-ray diffraction, susceptibility measurements, and Moessbauer spectroscopy. The results show that in this magnetite Mg is strongly substituted for Fe and the chemical formula is closer to MgFe{sub 2}O{sub 4} than Fe{sub 3}O{sub 4}. Magnetite also contains Mn, Ca, and Si elements, but at a lower proportion. The results are compatible with the chemical formula Fe{sub 2.08}Mg{sub 0.75}Mn{sub 0.11}Ca{sub 0.04}Si{sub 0.02}O{sub 4} and crystallochemical formula [Fe{sup 2{minus}}{sub 0.92}Ca{sup 2+}{sub 0.06}Si{sup 4+}{sub 0.02}]{sup tetra}[Fe{sup 3+}Fe{sup 2+}{sub 0.16}Mg{sup 2+}{sub 0.73}Mn{sup 2+}{sub 0.11}]{sup octa}O{sub 4}, showing the cation distribution on octahedral and tetrahedral sites of the spinel structure. The reason Mg element is not incorporated in soluble surface salt and in glass composition of the silico-aluminous fly ashes is now understood.

  16. Correlations between mass activity and physicochemical properties of Fe/N/C catalysts for the ORR in PEM fuel cell via 57Fe Mössbauer spectroscopy and other techniques.

    PubMed

    Kramm, Ulrike I; Lefèvre, Michel; Larouche, Nicholas; Schmeisser, Dieter; Dodelet, Jean-Pol

    2014-01-22

    The aim of this work is to clarify the origin of the enhanced PEM-FC performance of catalysts prepared by the procedures described in Science 2009, 324, 71 and Nat. Commun. 2011, 2, 416. Catalysts were characterized after a first heat treatment in argon at 1050 °C (Ar) and a second heat treatment in ammonia at 950 °C (Ar + NH3). For the NC catalysts a variation of the nitrogen precursor was also implemented. (57)Fe Mössbauer spectroscopy, X-ray photoelectron spectroscopy, neutron activation analysis, and N2 sorption measurements were used to characterize all catalysts. The results were correlated to the mass activity of these catalysts measured at 0.8 V in H2/O2 PEM-FC. It was found that all catalysts contain the same FeN4-like species already found in INRS Standard (Phys. Chem. Chem. Phys. 2012, 14, 11673). Among all FeN4-like species, only D1 sites, assigned to FeN4/C, and D3, assigned to N-FeN2+2 /C sites, were active for the oxygen reduction reaction (ORR). The difference between INRS Standard and the new catalysts is simply that there are many more D1 and D3 sites available in the new catalysts. All (Ar + NH3)-type catalysts have a much larger porosity than Ar-type catalysts, while the maximum number of their active sites is only slightly larger after a second heat treatment in NH3. The large difference in activity between the Ar-type catalysts and the Ar + NH3 ones stems from the availability of the sites to perform ORR, as many sites of the Ar-type catalysts are secluded in the material, while they are available at the surface of the Ar + NH3-type catalysts.

  17. Coordination of Fe, Ga and Ge in high pressure glasses by Moessbauer, Raman and X-ray absorption spectroscopy, and geological implications

    NASA Technical Reports Server (NTRS)

    Fleet, M. E.; Henderson, G. S.; Herzberg, C. T.; Crozier, E. D.; Osborne, M. D.; Scarfe, C. M.

    1984-01-01

    For some time, it has been recognized that the structure of silicate liquids has a great bearing on such magma properties as viscosity, diffusivity, and thermal expansion and on the extrapolation of thermodynamic quantities outside of the experimentally measurable range. In this connection it is vital to know if pressure imposes changes in melt structure similar to the pressure-induced reconstructive transformations in crystals. In the present study on 1 bar and high pressure glasses, an investigation is conducted regarding the coordination of Fe(3+) in Fe silicate glasses by Moessbauer spectroscopy. Raman spectroscopy is employed to explore the coordinations of Ge(4+) in GeO2 glasses and of Ga(3+) in NaGa silicate glasses, while the coordination of Ga(3+) in NaGaSiO4 glasses is studied with the aid of methods of X-ray absorption spectroscopy.

  18. X-ray powder diffraction and 57Fe Mössbauer spectroscopy of synthetic trioctahedral micas {K}[Me3]

    NASA Astrophysics Data System (ADS)

    Redhammer, G. J.; Amthauer, G.; Lottermoser, W.; Bernroider, M.; Tippelt, G.; Roth, G.

    2005-11-01

    Trioctahedral 1 M micas have been synthesized along (pseudo)binary joins using hydrothermal techniques and controlled oxygen fugacities. Octahedrally coordinated iron in annite {K}[Fe3]studied by 57Fe Mössbauer spectroscopy. With increasing substitution of iron by smaller divalent cations the quadrupole splitting distribution (QSD) evolves from a broad bimodal distribution in annite to a smaller unimodal distribution in Mg2+ and Ni2+-rich samples so that for high substitution rates more regular local environments are dominating. These results, however, can not be interpreted in terms of an octahedral cation ordering scheme. For none of the micas investigated reliable Fe2+ M2/M1 area ratios can be extracted. fMoreover, the complete QSD is shifted towards higher quadrupole splitting values. Similar observations were obtained for substituting Fe2+ by Mg2+ and Ni2+ in tetra-ferri-annite free of octahedral coordinated trivalent cations. Unlike in the Al3+ bearing micas a third QSD component is missing which supports the claim that the appearance of this third QSD component is closely related to the presence of trivalent cations (Al3+, Fe3+) in octahedra coordination.

  19. An East to West Mineralogical Trend in Mars Exploration Rover Spirit Moessbauer Spectra of Home Plate

    NASA Technical Reports Server (NTRS)

    Schroder, C.; Di, K.; Morris, R. V.; Klingelhofer, G.; Li, R.

    2008-01-01

    Home Plate is a light-toned plateau approx.90 m in diameter within the Inner Basin of the Columbia Hills in Gusev crater on Mars. It is the most extensive exposure of layered bedrock encountered by Spirit to date, and it is composed of clastic rocks of moderately altered alkali basalt composition, enriched in some highly volatile elements. Textural observations suggest an explosive origin and geochemical observations favor volcanism, probably a hydrovolcanic explosion [1]. Since it first arrived at Home Plate on sol 744, Spirit has circumnavigated the plateau (Fig. 1) and is now, since sol 1410, resting at its Winter Haven 3 location at the north end of Home Plate. Results: The MER Moessbauer spectrometers determine Fe oxidation states, identify Fe-bearing mineral phases and quantify the distribution of Fe among oxidation states and mineral phases [2]. Moessbauer spectra of Home Plate bedrock were obtained in five different locations from nine different targets (Fig. 1): Barnhill Ace, Posey Manager, and James Cool Papa Bell Stars at the northwest side of Home Plate; Pesapallo, June Emerson, and Elizabeth Emery on the east side; Texas Chili on the south side; Pecan Pie on the west side; and Chanute on the north side.

  20. Moessbauer spectra of olivine-rich achondrites - Evidence for preterrestrial redox reactions

    NASA Technical Reports Server (NTRS)

    Burns, R. G.; Martinez, S. L.

    1991-01-01

    Moessbauer spectral measurements at 4.2 K were made on several ureilites and the two shergottites found in Antarctica, as well as two ureilite falls, three SNC meteorite falls, and two finds in order to distinguish products of preterrestrial redox reactions from phases formed during oxidative weathering on the earth. The spectra indicated that several ureilites contain major proportions of metallic iron, much of which resulted from preterrestrial carbon-induced reduction of ferrous iron in the outermost 10-100 microns of olivine grains in contact with carbonaceous material in the ureilites. The cryptocrystalline nature of these Fe inclusions in olivine renders the metal extremely vulnerable to aerial oxidation, even in ureilites collected as falls. It is inferred that the nanophase ferric oxides or oxyhydroxides identified in Brachina and Lafayette were produced by terrestrial weather of olivines before the meteorites were found. The absence of goethite in two olivine-bearing Antarctic shergottites suggests that the 2 percent ferric iron determined in their Moessbauer spectra also originated from oxidation on Mars.

  1. On the ‘centre of gravity’ method for measuring the composition of magnetite/maghemite mixtures, or the stoichiometry of magnetite-maghemite solid solutions, via 57Fe Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Fock, Jeppe; Bogart, Lara K.; González-Alonso, David; Espeso, Jose I.; Hansen, Mikkel F.; Varón, Miriam; Frandsen, Cathrine; Pankhurst, Quentin A.

    2017-07-01

    We evaluate the application of 57Fe Mössbauer spectroscopy to the determination of the composition of magnetite (Fe3O4)/maghemite (γ-Fe2O3) mixtures and the stoichiometry of magnetite-maghemite solid solutions. In particular, we consider a recently proposed model-independent method which does not rely on a priori assumptions regarding the nature of the sample, other than that it is free of other Fe-containing phases. In it a single parameter, {{\\overlineδ}\\text{RT}} —the ‘centre of gravity’, or area weighted mean isomer shift at room temperature, T  =  295  ±  5 K—is extracted by curve-fitting a sample’s Mössbauer spectrum, and is correlated to the sample’s composition or stoichiometry. We present data on high-purity magnetite and maghemite powders, and mixtures thereof, as well as comparison literature data from nanoparticulate mixtures and solid solutions, to show that a linear correlation exists between {{\\overlineδ}\\text{RT}} and the numerical proportion of Fe atoms in the magnetite environment: α   =  Femagnetite/Fetotal =≤ft({{\\overlineδ}\\text{RT}}-{δ\\text{o}}\\right)/m , where {δ\\text{o}}   =  0.3206  ±  0.0022 mm s-1 and m   =  0.2135  ±  0.0076 mm s-1. We also present equations to relate α to the weight percentage w of magnetite in mixed phases, and the magnetite stoichiometry x  =  Fe2+/Fe3+ in solid solutions. The analytical method is generally applicable, but is most accurate when the absorption profiles are sharp; in some samples this may require spectra to be recorded at reduced temperatures. We consider such cases and provide equations to relate \\overlineδ(T) to the corresponding α value.

  2. The miniaturised Moessbauer spectrometer MIMOS II: future developments.

    NASA Astrophysics Data System (ADS)

    Rodionov, D.; Blumers, M.; Klingelhöfer, G.; Bernhardt, B.; Fleischer, I.; Schröder, C.; Morris, R.; Girones Lopez, J.

    2007-08-01

    In January 2004, the first in situ extraterrestrial Mössbauer spectrum was received from the Martian surface. At the present time (May 2007) two Miniaturized Mössbauer Spectrometers (MIMOS II) on board of the two Mars Exploration Rovers "Spirit" and "Opportunity" continue to collect valuable scientific data. Both spectrometers are operational after more than 3 years of work. Originally, the mission was expected to last for 90 days. To date more than 600 spectra were obtained with a total integration time for both rovers exceeding 260 days. The MER mission has proven that Mössbauer spectroscopy is a valuable technique for the in situ exploration of extraterrestrial bodies and the study of Fe-bearing samples. The Mössbauer team at the University of Mainz has accumulated a lot of experience and learned many lessons during last three years. All that makes MIMOS II a feasible choice for the future missions to Mars and other targets. Currently MIMOS II is on the scientific payload of two missions: Phobos Grunt (Russian Space Agency) and ExoMars (European Space Agency). Phobos Grunt is scheduled to launch in 2009. The main goals of the mission are: a) Phobos regolith sample return, b) Phobos in situ study, c) Mars and Phobos remote sensing. MIMOS II will be installed on the arm of a landing module. Currently, we are manufacturing an engineering model for testing purposes. The ESA "ExoMars" mission involves the development of a MER-like rover with more complex scientific payload (Pasteur exobiology instruments, including a drilling system). Its aim is to further characterise the biological environment in preparation for robotic missions and eventually human exploration. Data from the mission will provide invaluable input to the field of exobiology - the study of the origin, the evolution and distribution of life in the universe. The launch date is scheduled for 2013. Like on MER, the MIMOS II instrument will be mounted on a robotic arm. Advanced and improved version of

  3. Fe-Bearing Phases Identified by the Moessbauer Spectrometers on the Mars Exploration Rovers: An Overview

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Klingelhoefer, G.; Rodionov, D.; Yen, A.; Gellert, R.

    2006-01-01

    The twin Mars Exploration Rovers Spirit and Opportunity have explored the martian surface at Gusev Crater (GC) and Meridiani Planum (MP), respectively, for about two Earth years. The Moessbauer (MB) spectrometers on both rovers have analyzed an aggregate of 200 surface targets and have returned to Earth information on the oxidation state of iron, the mineralogical composition of Febearing phases, and the distribution of Fe among oxidation states and phases at the two landing sites [1-7]. To date, 15 component subspectra (10 doublets and 5 sextets) have been identified and most have been assigned to mineralogical compositions. Two subspectra are assigned to phases (jarosite and goethite) that are marker minerals for aqueous processes because they contain hydroxide anion in their structures. In this paper, we give an overview of the Febearing phases identified and their distributions at Gusev crater and Meridiani Planum.

  4. Fe-Bearing Phases Indentified by the Moessbauer Spectrometers on the Mars Exploration Rovers: An Overview

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Klingelhoefer, G.; Ming, D. W.; Schroeder, C.; Rodionov, D.; Yen, A.; Gellert, R.

    2006-01-01

    The twin Mars Exploration Rovers Spirit and Opportunity have explored the martian surface at Gusev Crater (GC) and Meridiani Planum (MP), respectively, for about two Earth years. The Moessbauer (MB) spectrometers on both rovers have analyzed an aggregate of approx.200 surface targets and have returned to Earth information on the oxidation state of iron, the mineralogical composition of Fe-bearing phases, and the distribution of Fe among oxidation states and phases at the two landing sites [1-7]. To date, 15 component subspectra (10 doublets and 5 sextets) have been identified and most have been assigned to mineralogical compositions. Two subspectra are assigned to phases (jarosite and goethite) that are marker minerals for aqueous processes because they contain hydroxide anion in their structures. In this paper, we give an overview of the Febearing phases identified and their distributions at Gusev crater and Meridiani Planum.

  5. Moessbauer analysis of Lewisville, Texas, archaeological site lignite and hearth samples. Environmental geology notes

    SciTech Connect

    Shiley, R.H.; Hughes, R.E.; Cahill, R.A.; Konopka, K.L.; Hinckley, C.C.

    1985-01-01

    The Lewisville site, located in Denton County on the Trinity River north of Dallas, Texas, was thought to provide evidence of the earliest human activity in the western hemisphere. Radiocarbon dates of 37,000 to 38,000 B.P. determined for the site in the late 1950s conflicted with the presence of a Clovis point, which would fix the age of the site between 11,000 and 11,500 B.P. It was hypothesized (Johnson, 1982) that Clovis people were burning lignite from nearby outcrops: lignite in hearth residues would give older than actual ages by radiocarbon dating. X-ray diffraction and instrumental neutron-activation analysis proved inconclusive; however, Moessbauer spectroscopy indicated that hematite, a pyrite combustion product, was present in the ash. From this evidence the authors conclude that there is some support for the hypothesis.

  6. Development of the Fast Scintillation Detector with Programmable High Voltage Adjustment Suitable for Moessbauer Spectroscopy

    SciTech Connect

    Prochazka, R.; Frydrych, J.; Pechousek, J.

    2010-07-13

    This work is focused on a development of a compact fast scintillation detector suitable for Moessbauer spectroscopy (low energy X-ray/{gamma}-ray detection) where high counting rates are inevitable. Optimization of this part was necessary for a reliable function, better time resolution and to avoid a detector pulses pile-up effect. The pile-up effect decreases the measurement performance, significantly depends on the source activity and also on the pulse duration. Our new detection unit includes a fast scintillation crystal YAP:Ce, an R6095 photomultiplier tube, a high voltage power supply socket C9028-01 assembly, an AD5252 digital potentiometer with an I2C interface and an AD8000 ultra fast operation preamplifier. The main advantages of this solution lie in a short pulse duration (less than 200 ns), stable operation for high activities, programmable gain of the high voltage supply and compact design in the aluminum housing.

  7. Interpretation of the Moessbauer Spectra of the Magnetic Nanoparticles in Mouse Spleen

    SciTech Connect

    Chuev, Mikhail A.; Cherepanov, Valery M.; Polikarpov, Mikhail A.; Panchenko, Vladislav Y.; Deyev, Sergey M.; Mischenko, Iliya N.; Nikitin, Maxim P.

    2010-12-02

    We have developed a stochastic model for description of relaxation effects in the system of homogeneously magnetized single-domain particles and applied the model to the analysis of Moessbauer spectra of magnetic nanoparticles (Chemicell ARA) and mouse spleen after i.v. injection into animals. We estimate that the fraction of exogenous iron in nanoparticles in the mouse spleen 3 months after injection was 0.27{+-}0.03. The spectra of the residual nanoparticles in the spleen had almost the same isomer shift but smaller mean hyperfine magnetic field values indicating decrease in the magnetic anisotropy energy (size) of the particles compared to the initial ones in the course of biodegradation. Concentration of ferritin-like iron was about three-fold higher than that in the spleen of untreated animals showing ferritin-like forms in the mouse spleen.

  8. Mineralogy at Gusev Crater and Meridiani Planum from the Moessbauer Spectrometers on the Mars Exploration Rovers

    NASA Technical Reports Server (NTRS)

    Morris, Richard V.; Klingelhoefer, Goestar

    2006-01-01

    The Moessbauer spectrometers on the twin MER rovers Spirit and Opportunity have provided significant new information on the distribution of iron among its oxidation states, the identification of the mineralogical composition of iron-bearing phases, and the distribution of iron among those phases for rock and soil at Gusev Crater and Meridiani Planum. The plains of Gusev Crater are dominated by olivine-bearing basalt (approximately Fo(60)) and Fe(3+)/Fe(total)=0.1 - 0.5. The oxide mineral generally present is magnetite. In contrast, initial results for the Columbia Hills are consistent with the presence of hematite and a ferrous iron phase, possibly pyroxene. Gusev spectra also have a ferric doublet (not jarosite) that is tentatively associated with nano-phase ferric oxide. A wider diversity of material is present at Meridiani Planum. Significantly, jarosite-bearing outcrop is present throughout the region, with good exposures in impact craters such as Eagle and Endurance (Fe(3+)/Fe (total) approx. 0.9). The Moessbauer identification of jarosite (a hydroxyl-bearing sulfate mineral) is evidence for aqueous, acid-sulfate processes on Mars. Hematite is observed within the outcrop matrix and in the spheroidal particles (Blueberries) found within the outcrop and as a surface lag. An isolated rock (Bounce Rock) was the only sample at either landing site whose iron-bearing phase was dominated by pyroxene. The basaltic sand in the central portion of Eagle crater, in the intercrater plains, and between slabs of outcrop at both Eagle and Endurance craters is olivine-bearing basalt. The widespread occurrence of olivine-bearing basalt at both MER landing sites implies that physical, rather than chemical, weathering processes dominate at the surface of contemporary Mars.

  9. Mineralogy at Gusev Crater and Meridiani Planum from the Moessbauer Spectrometers on the Mars Exploration Rovers

    NASA Technical Reports Server (NTRS)

    Morris, Richard V.; Klingelhoefer, Goestar

    2006-01-01

    The Moessbauer spectrometers on the twin MER rovers Spirit and Opportunity have provided significant new information on the distribution of iron among its oxidation states, the identification of the mineralogical composition of iron-bearing phases, and the distribution of iron among those phases for rock and soil at Gusev Crater and Meridiani Planum. The plains of Gusev Crater are dominated by olivine-bearing basalt (approximately Fo(60)) and Fe(3+)/Fe(total)=0.1 - 0.5. The oxide mineral generally present is magnetite. In contrast, initial results for the Columbia Hills are consistent with the presence of hematite and a ferrous iron phase, possibly pyroxene. Gusev spectra also have a ferric doublet (not jarosite) that is tentatively associated with nano-phase ferric oxide. A wider diversity of material is present at Meridiani Planum. Significantly, jarosite-bearing outcrop is present throughout the region, with good exposures in impact craters such as Eagle and Endurance (Fe(3+)/Fe (total) approx. 0.9). The Moessbauer identification of jarosite (a hydroxyl-bearing sulfate mineral) is evidence for aqueous, acid-sulfate processes on Mars. Hematite is observed within the outcrop matrix and in the spheroidal particles (Blueberries) found within the outcrop and as a surface lag. An isolated rock (Bounce Rock) was the only sample at either landing site whose iron-bearing phase was dominated by pyroxene. The basaltic sand in the central portion of Eagle crater, in the intercrater plains, and between slabs of outcrop at both Eagle and Endurance craters is olivine-bearing basalt. The widespread occurrence of olivine-bearing basalt at both MER landing sites implies that physical, rather than chemical, weathering processes dominate at the surface of contemporary Mars.

  10. Design and Construction of an Autonomous Low-Cost Pulse Height Analyzer and a Single Channel Analyzer for Moessbauer Spectroscopy

    SciTech Connect

    Velasquez, A.A.; Trujillo, J.M.; Morales, A.L.; Tobon, J.E.; Gancedo, J.R.; Reyes, L.

    2005-04-26

    A multichannel analyzer (MCA) and a single channel-analyzer (SCA) for Moessbauer spectrometry application have been designed and built. Both systems include low-cost digital and analog components. A microcontroller manages, either in PHA or MCS mode, the data acquisition, data storage and setting of the pulse discriminator limits. The user can monitor the system from an external PC through the serial port with the RS232 communication protocol. A graphic interface made with the LabVIEW software allows the user to adjust digitally the lower and upper limits of the pulse discriminator, and to visualize as well as save the PHA spectra in a file. The system has been tested using a 57Co radioactive source and several iron compounds, yielding satisfactory results. The low cost of its design, construction and maintenance make this equipment an attractive choice when assembling a Moessbauer spectrometer.

  11. Hyperfine Field Properties of Amorphous Iron-Germanium Alloys Through Moessbauer Spectroscopy Down to 0.72 K

    NASA Astrophysics Data System (ADS)

    Hamdeh, Hussein Husni

    Sputtered amorphous samples of FexGel-x; 0.12 < x < 0.72 have been studied by 57Fe Mossbauer spectroscopy over a temperature range from 0.72 K to room temperature. The broadening observed in the Mossbauer spectra lines is analyzed in terms of distributions of hyperfine fields. The isomer shift, the quadrupole splitting ((DELTA) Eq)(,eff) and the magnetic hyperfine field H(,eff) have been determined as functions of x and T. Also the magnetic ordering temperatures Tc have been determined for appropriate Fe concentrations. The critical concentration Xc below which magnetic ordering is absent down to 4.2 K has been found by extrapolating H(,eff)(x) or Tc(x) to zero to be around x = 0.43. The resulting analysis of the isomer shift suggests that the reduction of magnetism is caused mainly by the broadening process of the 3d-band and depends on the volume of the metalliod. The isomer shift data has a maximum around x = 0.55, and it is interpreted in terms of charge transfer, intra-atomic s (--->) d charge conversion and hybridization effects by a model proposed by Miedema and van der Woude. At room temperature the onset of long range magnetic order occurs around x = 0.52. Above Tc the observed ((DELTA) Eq)(,eff) is of order 0.45, whereas the average ((DELTA) Eq)(,eff) is zero below Tc. This indicates the random orientation of the electric field axes with respect to the magnetic hyperfine field. Both values show very slight variation with x and T. H(,eff) and Tc rise sharply with Fe concentration near and above Xc. The data are discussed in terms of localized moment and itinerant electron models. The relation between H(,eff) and the isomer shift has been established, and based on the general-band filling relation the isomer shift attains its maximum value when M(,eff) = m - 0.82n. The magnetic hyperfine field distributions P(H) have been determined as a function of T. They exhibit wide structureless shape and are considered to scale directly with the fraction distribution

  12. Moessbauer spectra as a 'fingerprint' in tin-lithium compounds: Applications to Li-ion batteries

    SciTech Connect

    Robert, F. Lippens, P.E.; Olivier-Fourcade, J.; Jumas, J.-C.; Gillot, F.; Morcrette, M.; Tarascon, J.-M.

    2007-01-15

    Several Li-Sn crystalline phases, i.e. Li{sub 2}Sn{sub 5}, LiSn, Li{sub 7}Sn{sub 3}, Li{sub 5}Sn{sub 2}, Li{sub 13}Sn{sub 5}, Li{sub 7}Sn{sub 2} and Li{sub 22}Sn{sub 5} were prepared by ball-milling and characterized by X-ray powder diffraction and {sup 119}Sn Moessbauer spectroscopy. The analysis of the Moessbauer hyperfine parameters, i.e. isomer shift ({delta}) and quadrupole splitting ({delta}), made it possible to define two types of Li-Sn compounds: the Sn-richest compounds (Li{sub 2}Sn{sub 5}, LiSn) and the Li-richest compounds (Li{sub 7}Sn{sub 3}, Li{sub 5}Sn{sub 2}, Li{sub 13}Sn{sub 5}, Li{sub 7}Sn{sub 2}, Li{sub 22}Sn{sub 5}). The isomer shift values ranged from 2.56 to 2.38 mm s{sup -1} for Li{sub 2}Sn{sub 5}, LiSn and from 2.07 to 1.83 mm s{sup -1} for Li{sub 7}Sn{sub 3}, Li{sub 5}Sn{sub 2}, Li{sub 13}Sn{sub 5}, Li{sub 7}Sn{sub 2} and Li{sub 22}Sn{sub 5}, respectively. A {delta}-{delta} correlation diagram is introduced in order to identify the different phases observed during the electrochemical process of new Sn-based materials. This approach is illustrated by the identification of the phases obtained at the end of the first discharge of {eta}-Cu{sub 6}Sn{sub 5} and SnB{sub 0.6}P{sub 0.4}O{sub 2.9}. - Graphical abstract: {delta}-{delta} correlation diagram for the different tin sites of the Li-Sn compounds. The symbols denote the different Li-Sn phases and the products obtained at the end of the discharge of {eta}-Cu{sub 6}Sn{sub 5} and SnB{sub 0.6}P{sub 0.4}O{sub 2.9}. The grey and the light-grey areas show Sn-centred polyhedra without and with one Sn first-nearest neighbours, respectively.

  13. Iron Mineralogy and Aqueous Alteration on Mars from the MER Moessbauer Spectrometers. Chapter 15

    NASA Technical Reports Server (NTRS)

    Morris, Richard V.; Klingelhoefer, Goestar

    2007-01-01

    The twin Mars Exploration Rovers Spirit (Gusev crater) and Opportunity (Meridiani Planum) used MIMOS II Moessbauer spectrometers to analyze martian surface materials in the first application of extraterrestrial Moessbauer spectroscopy. The instruments acquired spectra that identified the speciation of Fe according to oxidation state, coordination state, and mineralogical composition and provided quantitative information about the distribution of Fe among oxidation states, coordination states, and Fe-bearing phases. A total of 12 unique Fe-bearing phases were identified: Fe(2+) in olivine, pyroxene, and ilmenite; Fe(2+) and Fe(3+) in magnetite and chromite; Fe(3+) in nanophase ferric oxide (npOx), hematite, goethite, jarosite, an unassigned Fe3+ sulfate, and an unassigned Fe(3+) phase associated with jarosite; and Fe(0) in kamacite. Weakly altered basalts at Gusev crater (SO3 = 2.5 +/- 1.4 wt.% and Fe(3+)/Fe(sub T) = 0.24 +/- 0.11) are widespread on the Gusev plains and occur in less abundance on West Spur and Husband Hill in the Columbia Hills. Altered low-S rocks (SO3 = 5.2 +/- 2.0 wt.% and Fe(3+)/Fe(sub T) = 0.63 +/- 0.18) are the most common type of rock in the Columbia Hills. Ilm-bearing, weakly altered basalts were detected only in the Columbia Hills, as was the only occurrence of chromite in an altered low-S rock named Assemblee. Altered high-S rocks (SO3 > 14.2 wt.% and Fe(3+)/Fe(sub T) = 0.83 +/- 0.05) are the outcrop rocks of the ubiquitous Burns formation at Meridiani Planum. Two Fe(0)-bearing rocks at Meridiani Planum (Barberton and Heat Shield Rock) are meteorites. Laguna Class soil is weakly altered (SO3 = 6 +/- 2 wt.% and Fe(3+)/Fe(sub T) = 0.29 +/- 0.08) and widely distributed at both Gusev crater and Meridiani Planum, implying efficient global mixing processes or a global distribution of precursor rocks with comparable Fe mineralogical compositions. Paso Robles Class soil is heavily altered (SO3 approx. 31 wt.% and Fe(3+)/Fe(sub T) = 0.83 +/- 0

  14. Moessbauer Mineralogical Evidence for Aqueous Processes at Gusev Crater and Meridiani Planum

    NASA Astrophysics Data System (ADS)

    Morris, R. V.; Klingelhoefer, G.

    2004-12-01

    The Moessbauer spectrometers on the MER rovers have measured the relative abundances of iron with respect to both oxidation state and iron-bearing phase at Gusev Crater (Spirit rover) and Meridiani Planum (Opportunity rover). The assemblage of phases indicates aqueous alteration processes at both landing sites. Although the rock and soil of the Gusev Crater plains are dominated by Fe(2+) in olivine-bearing basalt (~Fo60), a Fe(3+)-rich component (nanophase ferric oxide, np-Ox) has significant abundance in surface soils (13-28% of total Fe) and in the surface coatings (rinds) of certain rocks (39%) but not in rock interiors exposed by grinding (5-6%). The mode of occurrence of np-Ox implies that it is the product of oxidative alteration of Fe(2+) silicate and oxide phases in the presence of H2O. The ubiquitous presence of sulfur in soil and in rock coatings, as determined by the MER-A APXS instrument, suggests that the alteration occurred under acid-sulfate conditions, so that both hydrolytic and sulfatic reactions are viable. A possible source for the weathering agents is volcanic emanations rich in H2O and SO2. Generally, rocks in the Columbia Hills are significantly more altered than those in the Gusev plains, with a higher proportion of Fe(3+) oxide phases compared to Fe(2+) silicate phases. This mineralogical dichotomy implies a difference in the timing, rate, duration, and/or mechanism of alteration for basaltic material in the Gusev plains compared to basaltic material in the Columbia Hills. It is possible, for example, that the basaltic material in the Columbia Hills underwent aqueous alteration in a paleoclimate that favored nearly complete alteration and that the basaltic material of the Gusev plains will not achieve the degree of alteration exhibited by the Columbia Hills under current martian surface conditions. Because its structure contains the hydroxide anion, the Moessbauer detection of the hydroxide sulfate jarosite (K,Na)Fe3(SO4)2(OH)6 in outcrops

  15. Moessbauer Mineralogical Evidence for Aqueous Processes at Gusev Crater and Meridiani Planum

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Klingelhoefer, G.

    2006-01-01

    The Moessbauer spectrometers on the MER rovers have measured the relative abundances of iron with respect to both oxidation state and iron-bearing phase at Gusev Crater (Spirit rover) and Meridiani Planum (Opportunity rover). The assemblage of phases indicates aqueous alteration processes at both landing sites. Although the rock and soil of the Gusev Crater plains are dominated by Fe(2+) in olivine-bearing basalt (approx.Fo60), a Fe(3+)-rich component (nanophase ferric oxide, np-Ox) has significant abundance in surface soils (13-28% of total Fe) and in the surface coatings (rinds) of certain rocks (39%) but not in rock interiors exposed by grinding (5-6%). The mode of occurrence of np-Ox implies that it is the product of oxidative alteration of Fe(2+) silicate and oxide phases in the presence of H2O. The ubiquitous presence of sulfur in soil and in rock coatings, as determined by the MER-A APXS instrument, suggests that the alteration occurred under acid-sulfate conditions, so that both hydrolytic and sulfatic reactions are viable. A possible source for the weathering agents is volcanic emanations rich in H2O and SO2. Generally, rocks in the Columbia Hills are significantly more altered than those in the Gusev plains, with a higher proportion of Fe(3+) oxide phases compared to Fe(2+) silicate phases. This mineralogical dichotomy implies a difference in the timing, rate, duration, and/or mechanism of alteration for basaltic material in the Gusev plains compared to basaltic material in the Columbia Hills. It is possible, for example, that the basaltic material in the Columbia Hills underwent aqueous alteration in a paleoclimate that favored nearly complete alteration and that the basaltic material of the Gusev plains will not achieve the degree of alteration exhibited by the Columbia Hills under current martian surface conditions.

  16. Moessbauer Mineralogical Evidence for Aqueous Processes at Gusev Crater and Meridiani Planum

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Klingelhoefer, G.

    2006-01-01

    The Moessbauer spectrometers on the MER rovers have measured the relative abundances of iron with respect to both oxidation state and iron-bearing phase at Gusev Crater (Spirit rover) and Meridiani Planum (Opportunity rover). The assemblage of phases indicates aqueous alteration processes at both landing sites. Although the rock and soil of the Gusev Crater plains are dominated by Fe(2+) in olivine-bearing basalt (approx.Fo60), a Fe(3+)-rich component (nanophase ferric oxide, np-Ox) has significant abundance in surface soils (13-28% of total Fe) and in the surface coatings (rinds) of certain rocks (39%) but not in rock interiors exposed by grinding (5-6%). The mode of occurrence of np-Ox implies that it is the product of oxidative alteration of Fe(2+) silicate and oxide phases in the presence of H2O. The ubiquitous presence of sulfur in soil and in rock coatings, as determined by the MER-A APXS instrument, suggests that the alteration occurred under acid-sulfate conditions, so that both hydrolytic and sulfatic reactions are viable. A possible source for the weathering agents is volcanic emanations rich in H2O and SO2. Generally, rocks in the Columbia Hills are significantly more altered than those in the Gusev plains, with a higher proportion of Fe(3+) oxide phases compared to Fe(2+) silicate phases. This mineralogical dichotomy implies a difference in the timing, rate, duration, and/or mechanism of alteration for basaltic material in the Gusev plains compared to basaltic material in the Columbia Hills. It is possible, for example, that the basaltic material in the Columbia Hills underwent aqueous alteration in a paleoclimate that favored nearly complete alteration and that the basaltic material of the Gusev plains will not achieve the degree of alteration exhibited by the Columbia Hills under current martian surface conditions.

  17. Moessbauer Spectroscopy for Lunar Resource Assessment: Measurement of Mineralogy and Soil Maturity

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Agresti, D. G.; Shelfer, T. D.; Pimperl, M. M.; Shen, M.-H.; Gibson, M. A.; Wills, E. L.

    1992-01-01

    First-order assessment of lunar soil as a resource includes measurement of its mineralogy and maturity. Soils in which the mineral ilmenite is present in high concentrations are desirable feedstock for the production of oxygen at a lunar base. The maturity of lunar soils is a measure of their relative residence time in the upper 1 mm of the lunar surface. Increasing maturity implies increasing load of solar wind species (e.g., N, H, and He-3), decreasing mean grain size, and increasing glass content. All these physicochemical properties that vary in a regular way with maturity are important parameters for assessing lunar soil as a resource. For example, He-3 can be extracted and potentially used for nuclear fusion. A commonly used index for lunar soil maturity is I(sub s)/FeO, which is the concentration of fine-grained metal determined by ferromagnetic resonance (I(sub s)) normalized to the total iron content (as FeO). I(sub s)/FeO has been measured for virtually every soil returned by the Apollo and Luna missions to the Moon. Because the technique is sensitive to both oxidation state and mineralogy, iron Moessbauer spectroscopy (FeMS) is a viable technique for in situ lunar resource assessment. Its utility for mineralogy is apparent from examination of published FeMS data for lunar samples. From the data published, it can be inferred that FeMS data can also be used to determine soil maturity. The use of FeMS to determine mineralogy and maturity and progress on development of a FeMS instrument for lunar surface use are discussed.

  18. Characterization of carbonitrided and oxidized layers on low-carbon steel by conversion electron Moessbauer spectrometry, X-ray diffractometry, and X-ray photoelectron spectrometry

    SciTech Connect

    Kurosawa, K.; Li, H.L.; Ujihira, Y.; Nomura, K.

    1999-03-01

    The structures of low-carbon steel oxidized in an aqueous saline bath at 403 K and a fused salt bath at 673 K after carbonitriding were studied using conversion electron Moessbauer spectrometry (CEMS), x-ray diffractometry (XRD), and x-ray photoelectron spectrometry (XPS). Only a doublet peak caused by poor crystallinity of iron oxyhydroxides (FeOOH) or fine particles of iron oxides such as magnetite (Fe{sub 3}O{sub 4}) and maghemite ({gamma}-Fe{sub 2}O{sub 3}) was detected in the CEMS spectra of the surface of the carbonitrided steel oxidized in the aqueous saline bath. Corrosion resistance of the carbonitrided specimens was increased by oxidizing. The oxidized layers produced in the aqueous saline bath were superior to those produced in the fused salt bath as a result of pores in the carbonitrided zone being filled with finer particles of iron oxides and the production of tight, thick oxide layers of amorphous iron oxyhydroxides or fine iron oxides. Deformation of iron nitride ({gamma}{prime}-Fe{sub 4}N) crystals in the carbonitrided zone could not be detected by oxidizing in the aqueous saline bath but were detected in the fused salt bath at 673 K.

  19. The Role of Iron in the Enhancement of Negative Magnetoresistance in La0.8Sr0.2FexCo1-xO3-z

    SciTech Connect

    Nemeth, Z.; Homonnay, Z.; Vertes, A.; Hakl, J.; Vad, K.; Meszaros, S.; Lackner, B.; Kellner, K.; Gritzner, G.; Greneche, J.M.; Lindbaum, A.

    2005-04-26

    The role of iron in enhancing the magnetoresistance in the compounds La0.8Sr0.2FexCo1-xO3-z was investigated by studying the electronic and magnetic structure of La0.8Sr0.2FexCo1-xO3-z as a function of temperature. For this purpose 57Fe transmission Moessbauer spectroscopy, magnetoresistance, as well as AC and DC magnetization measurements were applied. The detailed study of the temperature dependence of 57Fe Moessbauer parameters gave possibility to explore correlations between the local electronic and magnetic state of iron and the magnetic susceptibility as well as magnetoresistance in La0.8Sr0.2FexCo1-xO3-z. On the basis of the obtained results an attempt was made to explain the exotic magnetic and MR properties of these perovskites.

  20. Local environment of iron in heavy ion-irradiated amorphous magnetic oxides by Moessbauer and x-ray absorption spectroscopy

    SciTech Connect

    Studer, F.; Houpert Ch. ); Toulemonde, M. ) Dartyge E. )

    1991-04-01

    Moessbauer and X-ray absorption spectroscopies of some crystallized iron oxides, Fe{sub 2}O{sub 3}, FePO{sub 4}, Fe{sub 3}PO{sub 7}, and SrMn{sub 1.85}Fe{sub 0.15}O{sub 2.5}, the garnet Y{sub 3}Fe{sub 5}O{sub 12}, and the barium hexaferrite BaFe{sub 12}O{sub 19} have been undertaken in order to look at the local order around iron in Y{sub 3}Fe{sub 5}O{sub 12} and BaFe{sub 12}O{sub 19} materials amorphized by irradiation with high energy (27 MeV/n) xenon ions accelerated by GANIL. Simulations of the Moessbauer spectra suggested the presence of fivefold coordinated iron in the amorphous irradiated compounds with a distribution of magnetic interactions due to the variations of the number of iron second neighbors. The XANES spectra at the Fe-K edge confirmed the fivefold coordination of iron in the amorphous ferrites, show that the local structure around iron appears to be similar although the original structures were different, and appear close to the one observed in the Fe{sub 3}PO{sub 7} compound in which iron stands in a trigonal bipyramidal environment.

  1. Influence of ordering phenomena on the magnetostriction of high Si alloys for electrical applications

    SciTech Connect

    Ros-Yanez, Tanya; Ruiz, Daniel; Lopez, Diego; Hilgert, Tom; Dupre, Luc; Vandenberghe, Robert E.; Houbaert, Yvan

    2005-05-15

    The present work attempts to assess the influence of order phenomena on the magnetostriction of high Fe-Si alloys for electrical applications. The magnetostriction of high silicon electrical steels in the range of 4 to 6 wt. % Si was studied regarding the effect of processing and thermal treatment. In addition, power losses and saturation magnetization measurements were performed and {sup 57}Fe Moessbauer spectroscopy was used to evaluate and quantify the degree of order.

  2. Mössbauer study of some Argentinian chlorites

    NASA Astrophysics Data System (ADS)

    Gregori, Daniel A.; Mercader, R. C.

    1994-12-01

    Three chlorite samples obtained from mining areas in Mendoza, Argentina, have been studied by wet chemical analysis, X-ray diffraction and57Fe Mössbauer spectroscopy. The total Fe contents and the Fe2+/Fe3+ atomic ratio are used to characterize the samples and are discussed in connection to the likely genesis of the minerals.

  3. Combined Backscatter Moessbauer Spectrometer and X Ray Fluorescence analyzer (BaMS/XRF) for planetary surface materials

    NASA Technical Reports Server (NTRS)

    Agresti, D. G.; Shelfer, T. D.; Pimperl, M. M.; Wills, E. L.; Morris, R. V.

    1991-01-01

    A backscatter Moessbauer spectrometer (BaMS) with included x ray fluorescence (XRF) capability for the Mars Environment Survey (MESUR) Mission, which has been proposed by NASA for 1998, is being developed. The instrument will also be suitable for other planetary missions such as those to the Moon, asteroids, and other solid solar-system objects. The BaMS would be unique for MESUR in providing information about iron mineralogy in rocks, clays, and other surface materials, including relative proportions of iron-bearing minerals. It requires no sample preparation and can identify all the normal oxidation states of iron (3+, 2+, 0). Thus, BaMS is diagnostic for weathering and other soil-forming processes. Backscatter design allows the addition of XRF elemental analysis with little or no modification. The BaMS/XRF instrument complements the thermal analyzer with evolved gas analyzer (TA-EGA) and the alpha-proton x-ray spectrometer (APXS) proposed (along with BaMS) for geochemical analysis on MESUR.

  4. The Incredible Diversity of Fe-bearing Phases at Gusev Crater, Mars, According to the Mars Exploration Rover Moessbauer Spectrometer

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Klingelhoefer, G.; Schroeder, C.; Rodionov, D. S.; Ming, D. W.; Yen, A.

    2006-01-01

    The Mars Exploration Rover (MER) Spirit landed on the plains of Gusev Crater on 4 January 2004. One primary scientific objective for the mission is to characterize the mineralogical and elemental composition of surface materials, searching for evidence of water and clues for assessing past and current climates and their suitability for life [1]. The role of the Moessbauer (MB) spectrometer on Spirit is to provide quantitative information about the distribution of Fe among its oxidation and coordination states, identification of Fe-bearing phases, and relative distribution of Fe among those phases. The speciation and distribution of Fe in Martian rock and soil constrains the primary rock types, redox conditions under which primary minerals crystallized, the extent of alteration and weathering, the type of alteration and weathering products, and the processes and environmental conditions for alteration and weathering. In this abstract, we discuss the incredible diversity of Fe-bearing phases detected by Spirit s MB instrument during its first 540 sols of exploration at Gusev crater [2,3].

  5. Phase analytical studies of industrial copper smelting slags. Part I: Silicate slags

    NASA Astrophysics Data System (ADS)

    Rüffler, R.; Dávalos, J.

    1998-12-01

    The pyrometallurgical extraction of copper from sulfide ore concentrates is determined by the behaviour of the associated iron during smelting. Hence, 57Fe Mössbauer spectroscopy is an attractive tool for studying the phases in silicate slags from German and Chilean smelting plants. Other methods used were ore microscopy, electron microprobe analysis, and X-ray powder diffraction.

  6. Moessbauer spectroscopy and magnetic characteristics of Zn{sub 1-x}Co{sub x}Fe{sub 2}O{sub 4} (x = 0-1) nanoparticles

    SciTech Connect

    Ghasemi, Ali; Sepelak, Vladimir; Shirsath, Sagar E.; Liu Xiaoxi; Morisako, Akimitsu

    2011-04-01

    Zn{sub 1-x}Co{sub x}Fe{sub 2}O{sub 4} (x = 0-1 in a step of 0.2) nanoparticles with different range of particle size including 5-10 nm and 200-250 nm have been prepared by sol-gel process. Moessbauer spectra at room temperature indicated that, with increasing cobalt content, there is a transition from paramagnetic to magnetically ordered-ferrimagnetic state. Magnetic properties were measured at 300 and 10 K using a Quantum Design MPMS-5S SQUID magnetometer. It was found that with an increase in cobalt content the saturation magnetization and coercivity increase.

  7. Hyperfine interactions in soybean and lupin oxy-leghemoglobins studied using Mössbauer spectroscopy with a high velocity resolution

    NASA Astrophysics Data System (ADS)

    Kumar, A.; Alenkina, I. V.; Zakharova, A. P.; Oshtrakh, M. I.; Semionkin, V. A.

    2015-04-01

    A comparative study of monomeric soybean and lupin leghemoglobins in the oxy-form was carried out using Mössbauer spectroscopy with a high velocity resolution at 90 K. The 57Fe hyperfine parameters of measured spectra were evaluated and compared with possible structural differences in the heme Fe(II)-O 2 bond.

  8. YPdSn and YPd{sub 2}Sn: Structure, {sup 89}Y solid state NMR and {sup 119}Sn Moessbauer spectroscopy

    SciTech Connect

    Hoeting, Christoph; Eckert, Hellmut; Langer, Thorsten; Schellenberg, Inga; Poettgen, Rainer

    2012-06-15

    The stannides YPdSn and YPd{sub 2}Sn were synthesized by high-frequency melting of the elements in sealed tantalum tubes. Both structures were refined on the basis of single crystal X-ray diffractometer data: TiNiSi type, Pnma, a=715.4(1), b=458.8(1), c=789.1(1) pm, wR2=0.0461, 510 F{sup 2} values, 20 variables for YPdSn and MnCu{sub 2}Al type, Fm3 Macron m, a=671.44(8), wR2=0.0740, 55 F{sup 2} values, 5 parameters for YPd{sub 2}Sn. The yttrium atoms in the new stannide YPdSn are coordinated by two tilted Pd{sub 3}Sn{sub 3} hexagons (ordered AlB{sub 2} superstructure). In the Heusler phase YPd{sub 2}Sn each yttrium atom has octahedral tin coordination and additionally eight palladium neighbors. The cubic site symmetry of yttrium is reflected in the {sup 119}Sn Moessbauer spectrum which shows no quadrupole splitting. In contrast, YPdSn shows a single signal at {delta}=1.82(1) mm/s subjected to quadrupole splitting of {Delta}E{sub Q}=0.93(1) mm/s. Both compounds have been characterized by high-resolution {sup 89}Y solid state NMR spectroscopy, which indicates the presence of strong Knight shifts. The spectrum of YPd{sub 2}Sn is characterized by an unusually large linewidth, suggesting the presence of a Knight shift distribution reflecting local disordering effects. The range of {sup 89}Y Knight shifts of several binary and ternary intermetallic yttrium compounds is briefly discussed. - Graphical abstract: YPdSn and YPd{sub 2}Sn: Structure, {sup 89}Y solid state NMR and {sup 119}Sn Moessbauer spectroscopy. Highlights: Black-Right-Pointing-Pointer Synthesis and structure of ternary stannides YPdSn and YPd{sub 2}Sn. Black-Right-Pointing-Pointer {sup 119}Sn Moessbauer spectroscopic investigation of YPdSn and YPd{sub 2}Sn. Black-Right-Pointing-Pointer {sup 89}Y solid state NMR of intermetallics.

  9. Innovative instrumentation for mineralogical and elemental analyses of solid extraterrestrial surfaces: The Backscatter Moessbauer Spectrometer/X Ray Fluorescence analyzer (BaMS/XRF)

    NASA Technical Reports Server (NTRS)

    Shelfer, T. D.; Morris, Richard V.; Nguyen, T.; Agresti, D. G.; Wills, E. L.

    1994-01-01

    We have developed a four-detector research-grade backscatter Moessbauer spectrometer (BaMS) instrument with low resolution x-ray fluorescence analysis (XRF) capability. A flight-qualified instrument based on this design would be suitable for use on missions to the surfaces of solid solar-system objects (Moon, Mars, asteroids, etc.). Target specifications for the flight instrument are as follows: mass less than 500 g; volumes less than 300 cu cm; and power less than 2 W. The BaMS/XRF instrument would provide data on the oxidation state of iron and its distribution among iron-bearing mineralogies and elemental composition information. This data is a primary concern for the characterization of extraterrestrial surface materials.

  10. Applications of Thin Film Interference Filters to the Moessbauer Filtering of Synchrotron Radiation.

    NASA Astrophysics Data System (ADS)

    Hung, Nguyen Viet

    1981-06-01

    Synchrotron radiation produced by high energy storage rings surpasses all natural Mossbauer sources in spectral brightness within a narrow Mossbauer slice ((GAMMA) (TURN) 10('-8) ev) in the 1(ANGSTROM) wavelength region by 2-4 orders of magnitude. Several methods have been suggested to filter out this intense beam of resonant photons, such as nuclear Bragg reflection and time filtering techniques. This thesis investigates a new interference technique for Mossbauer filtering of synchrotron radiation, the impedance matched grazing incidence films introduced by Hannon et al. We extend their initial study to account for photoabsorption and show new possibilities for the suppression of electronic reflection. In particular the impedance matched condition can still be satisfied even though the reflection amplitudes are now complex and the new damping stabilized solutions previously inaccessible in the zero absorption limit were investigated and compared to impedance-matched solutions. Furthermore we consider coating a resonant Fe('59) film on a nonresonant substrate for the impedance matched and damping stabilized cases as well as alternate types of interference filters such as the half wave films and the ultra thin films. Mossbauer isotopes with strong resonant scattering power in addition to FE('57), namely Sn('119) and Dy('161) are explored as very promising materials in the interference filter design. Potential applications of the intense filtered resonant radiation are also discussed. To test the plausibility of the interference filters in the event that the surfaces are less than ideally smooth, a semiquantitative treatment of the effects of surface irregularities on the reflection properties of real surfaces is presented.

  11. Effect of Cu and Zn Substitutions on MnSb Properties

    SciTech Connect

    Mitsiuk, V. I.; Ryzhkovskii, V. M.; Tkachenka, T. M.

    2008-10-28

    The NiAs-type solid solutions based on manganese antimonide Mn{sub 1.1}Sb with Zn or Cu (up to 10 at % of substituting component) have been studied by {sup 57}Fe Moessbauer spectroscopy. It has been shown that the replacement of the manganese antimonide by Cu or Zn does not appreciably affect the main Moessbauer parameters in comparison to those of the parent compound. Two different values of hyperfine magnetic field at Fe are present in all the samples and can be attributed to the metal atoms located in MeI and MeII positions. The substitution of Cu or Zn for manganese antimonide leads to the redistribution of the metal atoms between two cation sublattices.

  12. Structural evolution of Fe{sub 80}C{sub 20} alloy with alloying times

    SciTech Connect

    Yoo, Yong-Goo; Paek, Mun-Cheol; Greneche, J.M.; Yang, Dong-Seok; Yu, Seong-Cho

    2005-05-15

    The structural evolution of mechanically alloyed Fe-C alloys was studied as a function of alloying times. The effect of alloying time on local structural changes of Fe-C has been investigated by means of {sup 57}Fe Moessbauer spectrometry, extended x-ray-absorption fine structure (EXAFS), and x-ray diffraction (XRD). XRD pattern from 24 h alloyed Fe-C powder indicates at least the mixture of bcc-Fe and Fe{sub 3}C phases. Moessbauer spectra analysis reveals that bcc-Fe decreases to the detriment of Fe{sub 3}C phase with increasing alloying time, while both carbon-containing bcc-Fe and amorphouslike phase assigned to Fe located in grain boundaries (estimated at two atomic layers) remain alloying time independent. The variation of Fe{sub 3}C phase content is in a good agreement with that observed by EXAFS analysis.

  13. Evidence for pigmentary hematite on Mars based on optical, magnetic, and Moessbauer studies of superparamagnetic (nanocrystalline) hematite

    NASA Technical Reports Server (NTRS)

    Morris, Richard V.; Agresti, David G.; Newcomb, Jeffery A.; Shelfer, Tad D.; Lauer, Howard V., Jr.

    1989-01-01

    Samples containing variable amounts of superparamagnetic hematite (sp-Hm) were prepared by a method in which the sp-Hm particles were dispersed throughout larger particles of silica gel, and the optical and magnetic properties of these samples were compared with those of larger-diameter hematite (bulk-Hm). It is shown that the optical properties of sp-Hm are different from those of bulk-Hm. Implications of the results for mineralogical interpretations of spectral data for the Martian surface and its terrestrial analogues are discussed. It is concluded that features resulting from ferric iron in the Martian spectral data and the results of the Viking magnetic properties experiment are both consistent with hematite present as both sp-Hm and bulk-Hm; the hematite particles most likely occur in pigmentary form, i.e., as particles dispersed throughout the volume of a spectrally neutral material.

  14. Magnetite in Martian Meteorite Mil 03346 and Gusev Adirondack Class Basalt: Moessbauer Evidence for Variability in the Oxidation State of Adirondack Lavas

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; McKay, G. A.; Ming, D. W.; Klingelhoefer, G.; Schroeder, C.; Rodionov, D.; Yen, A.

    2006-01-01

    The Moessbauer spectrometers on the Mars Exploration Rovers Spirit (Gusev crater) and Opportunity (Meridiani Planum) have returned information on the oxidation state of iron, the mineralogical composition of Fe-bearing phases, and the distribution of Fe among oxidation states and phases [1,2,3]. To date, 100 and 85 surface targets have been analyzed by the Spirit and Opportunity spectrometers, respectively. Twelve component subspectra (8 doublets and 4 sextets) have been identified and most have been assigned to mineralogical compositions [4]. Two sextet subspectra result from the opaque and strongly magnetic mineral magnetite (Fe3O4 for the stoichiometric composition), one each for the crystallographic sites occupied by tetrahedrally-coordinated Fe3+ and by octahedrally-coordinated Fe3+ and Fe2+. At Gusev crater, the percentage of total Fe associated with magnetite for rocks ranges from 0 to 35% (Fig. 1) [3]. The range for soils (5 to 12% of total Fe from Mt, with one exception) is narrower. The ubiquitous presence of Mt in soil firmly establishes the phase as the strongly magnetic component in martian soil

  15. Magnetic, ferroelectric, and spin phonon coupling studies of Sr3Co2Fe24O41 multiferroic Z-type hexaferrite

    NASA Astrophysics Data System (ADS)

    Raju, N.; Shravan Kumar Reddy, S.; Ramesh, J.; Gopal Reddy, Ch.; Yadagiri Reddy, P.; Rama Reddy, K.; Sathe, V. G.; Raghavendra Reddy, V.

    2016-08-01

    The magnetic, Raman, ferroelectric, and in-field 57Fe Mössbauer studies of polycrystalline multiferroic Sr3Co2Fe24O41 are reported in this paper. From the magnetization studies, it is observed that the sample is soft magnetic in nature with low temperature magnetic spin transitions like longitudinal to transverse conical structure around 130 K and change in magnetic crystalline anisotropy from conical to planar structure at 250 K. Ferroelectric studies of the sample exhibit the spontaneous polarization at low temperature. Strong spin phonon and spin lattice coupling is observed through low temperature Raman spectroscopy. From the in-field 57Fe Mössbauer spectroscopy, spin up and spin down site occupations of Fe ions are calculated in the unit cell.

  16. Hydrogenation of FeCoZr-Al2O3 nanocomposites studied by Mössbauer spectroscopy and magnetometry

    NASA Astrophysics Data System (ADS)

    Saad, A.; Kasiuk, J.; Fedotova, J.; Szilagyi, E.; Przewoznik, J.; Kapusta, Cz.; Marszalek, M.

    2009-02-01

    Hydrogenation effects on crystalline and magnetic structure of nanocomposites (FeCoZr) x (Al2O3)100 - x , 38 ≤ x ≤ 63 at.% are studied by 57Fe Mössbauer spectroscopy and magnetometry. Variations of local structure, blocking temperature and mean FeCoZr nanoparticles’ volume are discussed with respect to (i) composition and (ii) two competing processes—H2 incorporation and annealing—occurred during treatment in H2 plasma.

  17. Structural and phase transformations during copper and iron mechanical alloying in liquid medium studied by Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Eryomina, Marina Anatol'evna; Lomayeva, Svetlana Fedorovna; Ul'yanov, Alexandr Leonidovich; Yelsukov, Evgeny Petrovich

    2016-03-01

    Mössbauer spectroscopy and X-ray diffraction have been used to study the kinetics of structural and phase transformations in Cu + 2 at% 57Fe during mechanical activation in liquid media (heptane, distilled water) and subsequent heat treatment (600 and 700 °C). The initial stages of mechanical alloying are associated with the transition of components to the nanostructural state. Iron atom groups form near the grain boundaries, and isolated iron atoms penetrate from the boundaries into the grains. Oxidation of groups of iron atoms that form highly dispersed phases of ternary oxide and magnetite occur in the initial stages of mechanical alloying of Cu + 2 at% 57Fe in water. The formation of the solid solution in the form of isolated iron atoms in the lattice of copper proceeds, regardless of the milling media used. Samples prepared in heptane contain carbon and oxygen, and upon heat treatment, carbide and oxide phases are formed.

  18. Magnetic, ferroelectric, and spin phonon coupling studies of Sr{sub 3}Co{sub 2}Fe{sub 24}O{sub 41} multiferroic Z-type hexaferrite

    SciTech Connect

    Raju, N.; Shravan Kumar Reddy, S.; Ramesh, J.; Gopal Reddy, Ch.; Yadagiri Reddy, P. Rama Reddy, K.; Sathe, V. G.; Raghavendra Reddy, V.

    2016-08-07

    The magnetic, Raman, ferroelectric, and in-field {sup 57}Fe Mössbauer studies of polycrystalline multiferroic Sr{sub 3}Co{sub 2}Fe{sub 24}O{sub 41} are reported in this paper. From the magnetization studies, it is observed that the sample is soft magnetic in nature with low temperature magnetic spin transitions like longitudinal to transverse conical structure around 130 K and change in magnetic crystalline anisotropy from conical to planar structure at 250 K. Ferroelectric studies of the sample exhibit the spontaneous polarization at low temperature. Strong spin phonon and spin lattice coupling is observed through low temperature Raman spectroscopy. From the in-field {sup 57}Fe Mössbauer spectroscopy, spin up and spin down site occupations of Fe ions are calculated in the unit cell.

  19. Exploration of synchrotron Mossbauer micrscopy with micrometer resolution: forward and a new backscattering modality on natural samples

    SciTech Connect

    Yan, L.; Zhao, J.; Toellner, T.S.; Divan, R.; Xu, S.; Cai, Z.; Boesenberg, J.S.; Freidrich, J.M.; Cramer, S.P.; Alp, E.E.

    2012-01-01

    New aspects of synchrotron Moessbauer microscopy are presented. A 5 {micro}m spatial resolution is achieved, and sub-micrometer resolution is envisioned. Two distinct and unique methods, synchrotron Moessbauer imaging and nuclear resonant incoherent X-ray imaging, are used to resolve spatial distribution of species that are chemically and magnetically distinct from one another. Proof-of-principle experiments were performed on enriched {sup 57}Fe phantoms, and on samples with natural isotopic abundance, such as meteorites.

  20. Magnetic anisotropy and sub-lattice magnetization study of polycrystalline magneto-electric GaFexO3

    NASA Astrophysics Data System (ADS)

    Raghavendra Reddy, V.; Sharma, Kavita; Gupta, Ajay; Banerjee, A.

    2014-08-01

    Polycrystalline magneto-electric GaFexO3 (0.8≤x≤1.2) ceramics are studied with bulk magnetization and 57Fe Mössbauer measurements. The ferrimagnetic to paramagnetic transition temperature (TC), saturation magnetization (MS) and the magnetic anisotropy values are found to vary significantly with the site-disorder of Fe3+ and Ga3+ cations. With the increase of iron content, increase of TC and MS, and decrease of magnetic anisotropy are observed. Using low temperature high magnetic field 57Fe Mössbauer measurements, individual temperature dependence of hyperfine fields and hence magnetization of the three sub-lattices are measured. It is observed that the three sub-lattices have quite a different temperature dependence resulting in the non-monotonous variation of resultant magnetization as measured by bulk magnetic measurements. Definite evidence, using 57Fe Mössbauer measurements, is submitted to show that the Fe ions at Fe2 and Ga2 sites are responsible for the observed magnetic anisotropy, site-disorder induced magnetism and thermo-magnetic irreversible features in GaFexO3.

  1. The structure and stability of CaFe layered double hydroxides with various Ca:Fe ratios studied by Mössbauer spectroscopy, X-ray diffractometry and microscopic analysis

    NASA Astrophysics Data System (ADS)

    Sipiczki, M.; Kuzmann, E.; Homonnay, Z.; Megyeri, J.; Pálinkó, I.; Sipos, P.

    2013-07-01

    The effects of the Ca(II)/Fe(III) ratios on the structure and Fe microenvironments have been studied in layered double hydroxides comprising of Ca(II) and Fe(III) (CaFe-LDH) prepared by the co-precipitation method. The Ca(II)/Fe(III) ratios were varied systematically from 2 to 6 and for characterisation 57Fe Mössbauer spectroscopy, powder X-ray diffractometry and scanning electron microscopy were applied. XRD patterns of the samples at all Ca(II)/Fe(III) ratios exhibited reflections corresponding to CaFe-LDH and 57Fe Mössbauer measurements revealed that Fe(III) was in a high-spin, somewhat disordered octahedral environment. Above the Ca(II)/Fe(III) ratio of 2 the reflections of Ca(OH)2 also appeared. This phase was found to stabilise the LDH phase, while the phase-pure LDH decomposed on ageing.

  2. Combined Raman-LIBS, Moessbauer and XRD In-Situ Mineral Analysis of Evaporite Minerals at Rio Tinto (Spain)

    NASA Astrophysics Data System (ADS)

    Rull, F.; Klingelhöfer, G.; Sarrazin, P.; Medina, J.; Fleischer, I.; Blake, D.; Martin Ramos, J. D.

    2010-04-01

    In this study a combination of Raman, LIBS, Mössbauer and XRD portable instruments has been used to undertake a common in-situ analysis of sulphate minerals at Rio Tinto area within the CAREX Field Procedure Inter-comparison Exercise 2009.

  3. Ultra-soft magnetic properties and correlated phase analysis by {sup 57}Fe Mössbauer spectroscopy of Fe{sub 74}Cu{sub 0.8}Nb{sub 2.7}Si{sub 15.5}B{sub 7} alloy

    SciTech Connect

    Manjura Hoque, S.; Liba, S. I.; Akhter, Shireen; Anirban, A.; Choudhury, Shamima

    2016-02-15

    A detailed study of magnetic softness has been performed on FINEMENT type of ribbons by investigating the BH loop with maximum applied field of 960 A/m. The ribbon with the composition of Fe{sub 74}Cu{sub 0.8}Nb{sub 2.7}Si{sub 15.5}B{sub 7} was synthesized by rapid solidification technique and the compositions volume fraction was controlled by changing the annealing condition. Detail phase analysis was performed through X-ray diffraction (XRD), Differential scanning calorimetry (DSC), Vibrating sample magnetometer (VSM) and Mössbauer spectroscopy in order to correlate the ultrasoft magnetic properties with the volume fraction of amorphous and α-Fe(Si) soft nano composites. Bright (BF) and dark field (DF) image with selective area diffraction (SAD) patterns by the transmission electron microscopy (TEM) of the sample annealed for the optimized annealed condition at 853 K for 3 min reveals nanocrystals with an average size between 10-15 nm possessing the bcc structure which matches with the grain size revealed by the X-ray diffraction. Kinetics of crystallization of α-Fe(Si) phases has been determined by DSC curves. Extremely small coercivity of 30.9 A/m and core loss of 2.5 W/Kg for the sample annealed at 853 K for 3 min was found. Similar values for other crystalline conditions were determined by using BH loop tracer with a maximum applied field of around 960 A/m. Mössbauer spectroscopy was used to determine chemical shift, hyperfine field distribution (HFD), and peak width of different phases. The volume fractions of the relative amount of amorphous and crystalline phases are also determined by Mössbauer spectroscopy. High saturation magnetization along with ultrasoft magnetic properties exhibits very high potentials technological applications.

  4. The 57Fe Mössbauer parameters of pyrite and marcasite with different provenances

    USGS Publications Warehouse

    Evans, B.J.; Johnson, R.G.; Senftle, F.E.; Cecil, C.B.; Dulong, F.

    1982-01-01

    The Mössbauer parameters of pyrite and marcasite exhibit appreciable variations, which bear no simple relationship to the geological environment in which they occur but appear to be selectively influenced by impurities, especially arsenic, in the pyrite lattice. Quantitative and qualitative determinations of pyrite/marcasite mechanical mixtures are straightforward at 298 K and 77 K but do require least-squares computer fittings and are limited to accuracies ranging from ±5 to ±15 per cent by uncertainties in the parameter values of the pure phases. The methodology and results of this investigation are directly applicable to coals for which the presence and relative amounts of pyrite and marcasite could be of considerable genetic significance.

  5. Magnetic ordering in57Fe-doped high- T c superconductors

    NASA Astrophysics Data System (ADS)

    Morrish, A. H.; Zhou, X. Z.; Luo, L. Y.; Li, Z. W.; Maartense, I.

    1990-07-01

    The high-temperature superconductor, Tl2CaBa2(Cu1- x Fe x )2O8+δ (the 2122 compound), has been investigated by a number of techniques, including X-ray diffraction, resistance and ac susceptibility measurements, and Mössbauer spectroscopy. The procedures followed to make close to single-phase samples are described. The decrease in the critical temperature for superconductivity, T c , is less than for the iron-doped 123 compounds. The Mössbauer spectra at 77 K and above consist of an asymmetric doublet. Below about 10 K magnetic hyperfine splitting occurs; relaxation effects are still present at 2.3 K. The spectra can be fitted with two overlapping patterns. Their origin is discussed: comparisons are made with other high- T c superconductors.

  6. MOKE Study of Fe/Co/Al Multilayers

    SciTech Connect

    Jani, Snehal; Lakshmi, N.; Venugopalan, K.; Rajput, Parasmani; Zajaoc, M.; Rueffer, R.; Reddy, V. R.; Gupta, Ajay

    2011-07-15

    The multilayer system (MLS)-[{sup 57}Fe{sub 25}A/Co{sub 11}A/Al{sub 17}A]x20 has been deposited by Ion beam sputtering (IBS) technique. The MLS has been annealed at 700 deg. C for 1 h. Overall composition of as deposited and annealed MLS have been characterized by EDX and magnetic properties have been studied through angular dependent magneto optic Kerr effect (MOKE) hysteresis curves. The study shows that the as-deposited MLS has excellent soft magnetic properties coupled with perpendicular magnetic isotropy which is destroyed on annealing.

  7. Application of 57Co emission Mössbauer spectroscopy to studying biocomplexes in frozen solutions

    NASA Astrophysics Data System (ADS)

    Kamnev, A. A.; Kulikov, L. A.; Perfiliev, Yu. D.; Antonyuk, L. P.; Kuzmann, E.; Vértes, A.

    2005-09-01

    Emission Mössbauer spectroscopy with the 57Co isotope was used to study very dilute rapidly frozen aqueous solutions of cobalt(II) complexes with low-molecular-weight biomolecules (aromatic amino acids anthranilic acid and L-tryptophan) and within a sophisticated biopolymer, bacterial glutamine synthetase, a key enzyme of nitrogen metabolism. The appearance of after-effects of the 57Co→57Fe nuclear transformation as well as the coordination properties of the cation and the ligands in the complexes are discussed on the basis of their Mössbauer parameters.

  8. Comparative study using MS and XRD of Fe80Al20 alloy produced by mechanical alloying

    NASA Astrophysics Data System (ADS)

    Hadef, F.; Otmani, A.; Grenèche, J. M.

    2013-08-01

    An X-ray diffraction and 57Fe Mössbauer effect study of mechanically alloyed Fe80Al20 is presented. X-ray measurements indicate that the disordered bcc α-Fe(Al) solid solution was formed after 2 h of milling, while the analysis of Mössbauer spectra suggested that total dissolution of aluminium is achieved after 10 h of milling. These differences can be attributed to: (i) rapid nanocrystallization of aluminium and/or (ii) small particles with small amounts of aluminium cannot be detected by the X-ray diffraction technique.

  9. Mössbauer study of EUROFER and VVER steel reactor materials

    NASA Astrophysics Data System (ADS)

    Kuzmann, E.; Horváth, Á.; Alves, L.; Silva, J. F.; Gomes, U.; Souza, C.; Homonnay, Z.

    2013-04-01

    57Fe Mössbauer spectroscopy and X-ray diffractometry were used to study EUROFER or VVER ferritic reactor steels mechanically alloyed with TaC or NbC. Significant changes were found in the Mössbauer spectra and in the corresponding hyperfine field distributions between the ball milled pure steel and that alloyed with TaC or NbC. Spectral differences were also found in the case of use of same carbides with different origin, too. The observed spectral changes as an effect of ball milling of the reactor material steels with carbides can be associated with change in short range order of the constituents of steel.

  10. Mössbauer study of iron uptake in cucumber root

    NASA Astrophysics Data System (ADS)

    Kovács, K.; Kuzmann, E.; Fodor, F.; Vértes, A.; Kamnev, A. A.

    2005-09-01

    57Fe Mössbauer spectroscopy was used to study the uptake and distribution of iron in the root of cucumber plants grown in iron-deficient modified Hoagland nutrient solution and put into iron-containing solution with 10 μM Fe citrate enriched with 57Fe (90%) only before harvesting. The Mössbauer spectra of the frozen roots exhibited two Fe3+ components with typical average Mössbauer parameters of δ = 0.5 mm s-1, Δ = 0.46 mm s-1 and δ = 0.5 mm s-1, Δ = 1.2 mm s-1 at 78 K and the presence of an Fe2+ doublet, assigned to the ferrous hexaaqua complex. This finding gives a direct evidence for the existence of Fe2+ ions produced via root-associated reduction according to the mechanism proposed for iron uptake for dicotyledonous plants. Monotonous changes in the relative content of the components were found with the time period of iron supply. The Mössbauer results are interpreted in terms of iron uptake and transport through the cell wall and membranes.

  11. Setting temperature effect in polycrystalline exchange-biased IrMn/CoFe bilayers

    SciTech Connect

    Fernandez-Outon, L. E.; Araujo Filho, M. S.; Araujo, R. E.; Ardisson, J. D.; Macedo, W. A. A.

    2013-05-07

    We study the effect of atomic interdiffusion on the exchange bias of polycrystalline IrMn/({sup 57}Fe + CoFe) multilayers due to the thermal setting process of exchange coupling during field annealing. Depth-resolved {sup 57}Fe conversion electron Moessbauer spectroscopy was used to quantify atomic interdiffusion. Vibrating sample magnetometry was used to monitor the variation of exchange bias and magnetisation. It was found that interface sharpness is only affected above {approx}350 Degree-Sign C. Three different stages for the setting of exchange bias can be inferred from our results. At the lower setting temperatures (up to 350 Degree-Sign C), the effect of field annealing involves alignment of spins and interfacial coupling due to the setting of both antiferromagnetic (AF) bulk and interface without significant interdiffusion. At a second stage (350-450 Degree-Sign C), where AF ordering dominates over diffusion effects, atomic migration and increased setting of AF spins co-exist to produce a peak in exchange bias field and coercivity. On a third stage (>450 Degree-Sign C), severe chemical intermixing reduces significantly the F/AF coupling.

  12. Moessbauer Mineralogy of Rock, Soil, and Dust at Gusev Crater, Mars: Spirit's Journey through Weakly Altered Olivine Basalt on the Plains and Pervasively Altered Basalt in the Columbia Hills

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Klingelhoefer, G.; Schroeder, C.; Rodionov, D. S.; Yen, A.; Ming, D. W.; deSouza, P. A., Jr.; Fleischer, I.; Wdowiak, T.; Gellert, R.; hide

    2006-01-01

    The Moessbauer spectrometer on Spirit measured the oxidation state of Fe, identified Fe-bearing phases, and measured relative abundances of Fe among those phases for surface materials on the plains and in the Columbia Hills of Gusev crater. Eight Fe-bearing phases were identified: olivine, pyroxene, ilmenite, magnetite, nanophase ferric oxide (npOx), hematite, goethite, and a Fe(3+)-sulfate. Adirondack basaltic rocks on the plains are nearly unaltered (Fe(3+)/Fe(sub T)<0.2) with Fe from olivine, pyroxene (Ol>Px), and minor npOx and magnetite. Columbia Hills basaltic rocks are nearly unaltered (Peace and Backstay), moderately altered (WoolyPatch, Wishstone, and Keystone), and pervasively altered (e.g., Clovis, Uchben, Watchtower, Keel, and Paros with Fe(3+)/Fe(sub T) approx.0.6-0.9). Fe from pyroxene is greater than Fe from olivine (Ol sometimes absent), and Fe(2+) from Ol+Px is 40-49% and 9-24% for moderately and pervasively altered materials, respectively. Ilmenite (Fe from Ilm approx.3-6%) is present in Backstay, Wishstone, Keystone, and related rocks along with magnetite (Fe from Mt approx. 10-15%). Remaining Fe is present as npOx, hematite, and goethite in variable proportions. Clovis has the highest goethite content (Fe from Gt=40%). Goethite (alpha-FeOOH) is mineralogical evidence for aqueous processes because it has structural hydroxide and is formed under aqueous conditions. Relatively unaltered basaltic soils (Fe(3+)/Fe(sub T) approx. 0.3) occur throughout Gusev crater (approx. 60-80% Fe from Ol+Px, approx. 10-30% from npOx, and approx. 10% from Mt). PasoRobles soil in the Columbia Hills has a unique occurrence of high concentrations of Fe(3+)-sulfate (approx. 65% of Fe). Magnetite is identified as a strongly magnetic phase in Martian soil and dust.

  13. Iron Isotope Variations in Reduced Groundwater and in Drinking Water Supplies: A Case Study of Hanoi, Vietnam

    NASA Astrophysics Data System (ADS)

    Teutsch, N.; Berg, M.; von Gunten, U.; Halliday, A.

    2004-12-01

    In reduced groundwater iron is involved in biotic and abiotic transformation processes, both of which could lead to iron isotope fractionation. The reduced groundwater aquifers in the area of the Vietnamese capital of Hanoi are the main drinking water sources for the city. These groundwaters contain arsenic, which imposes a serious health threat to millions of people. Dissolved arsenic is related to the reducing conditions prevalent in the groundwater, and iron and arsenic contents are correlated in the sediments. We are employing iron isotope composition as a tool to better understand the processes leading to the transformation of iron in the groundwater and its role in various biogeochemical processes in reduced environments. Drinking water is supplied to the city of Hanoi from several water treatment plants (WTP) which pump the raw groundwater from a lower aquifer, while the rural surroundings pump untreated groundwater from an upper aquifer by private tubewells. Surface water from the Red River delta is the main source of recharge to these two aquifers. Due to high content of particulate natural organic matter (NOM) in the sediment leading to extensive microbial activity, the groundwaters are anoxic and rich in dissolved iron(II). The iron(II) removal in the WTPs is carried by a multi-step treatment including aeration, settling, filtration, and chlorination. We have collected natural groundwater samples for isotopic analysis from two aquifers at several locations, a groundwater depth profile and its corresponding sediment phases from the upper aquifer and the underlying aquitard, raw and treated water from several WTPs, as well as the corresponding iron(III) precipitates. The iron concentrations of groundwaters analysed in this study range from 3 to 28 mg/L and δ 57Fe (57/54 deviation from IRMM 014) values vary between -1.2 and +1.5 ‰ . The sediment depth profile has a δ 57Fe around +0.3 ‰ , which implies that the high values obtained in the groundwater

  14. Oxidation and surface segregation of chromium in Fe-Cr alloys studied by Mössbauer and X-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Idczak, R.; Idczak, K.; Konieczny, R.

    2014-09-01

    The room temperature 57Fe Mössbauer and XPS spectra were measured for polycrystalline iron-based Fe-Cr alloys. The spectra were collected using three techniques: the transmission Mössbauer spectroscopy (TMS), the conversion electron Mössbauer spectroscopy (CEMS) and the X-ray photoelectron spectroscopy (XPS). The combination of these experimental techniques allows to determine changes in Cr concentration and the presence of oxygen in bulk, in the 300 nm pre-surface layer and on the surface of the studied alloys.

  15. Magnetic dilution of the iron sublattice in CoFe{sub 2-x}Sc{sub x}O{sub 4} (0{<=}x{<=}1)

    SciTech Connect

    Lefevre, C.; Roulland, F.; Viart, N.; Greneche, J.M.; Pourroy, G.

    2010-11-15

    Substitution of Fe for Sc in CoFe{sub 2}O{sub 4} spinel structure is presented. All CoFe{sub 2-x}Sc{sub x}O{sub 4} compounds crystallize in the spinel type structure (space group Fd3-bar m). By using X-ray diffraction studies, magnetic measurements and in-field {sup 57}Fe Moessbauer spectrometry, the limit of substitution has been determined to be equal to x=0.56. An increase in the cell parameter and the strains and a decrease in the apparent crystallites size are observed. For x>0.3, a partial oxidation of cobalt is evidenced and Co{sup 3+} is stabilized in the structure. A ferromagnetic behavior has been observed for all investigated compounds. As x increases, the Curie temperature and the hyperfine fields decrease. Following the Stephenson model, the diminution of T{sub C} is ascribed to a decrease of the main J{sub AB} interaction. -- Graphical abstract: Evolution of the cell parameters, the magnetic properties and the Moessbauer spectra in CoFe{sub 2-r}Sc{sub r}O{sub 4} (0{<=}r{<=}1). Display Omitted

  16. Modifications of the magnetic properties of ferrites by swift heavy ion irradiations

    SciTech Connect

    Costantini, Jean-Marc; Studer, Francis; Peuzin, Jean-Claude

    2001-07-01

    Single crystal plates of ferrimagnetic yttrium iron garnet (111)-YIG:Si (Y{sub 3}Fe{sub 4.94}Si{sub 0.06}O{sub 12}) and barium hexaferrite (00.1)-BaM (BaFe{sub 12}O{sub 19}) or (00.1)-BaM:Co,Ti (BaFe{sub 9.1}Co{sub 1.4}Ti{sub 1.5}O{sub 19}) are irradiated with swift heavy ions (3.8 GeV {sup 129}Xe or 6.0 GeV {sup 208}Pb) in the electronic slowing down regime, above the threshold ({approximately}20 keV nm{minus}1) of formation of continuous and homogeneous cylindrical amorphous tracks. The modifications of the magnetic properties are studied by {sup 57}Fe Moessbauer spectroscopy and ac magnetic permeability measurements versus ion fluence. In the doped crystals having a planar magnetic anisotropy (YIG:Si and BaM:Co,Ti), the room-temperature Moessbauer spectra show that the magnetization is flipped perpendicularly to the sample plane at a critical amorphous fraction around 30% in both compounds. This corresponds to a 90% drop of the measured in-plane magnetic permeability. No such effect is seen in the undoped BaM samples with the axial [00.1] anisotropy. These data are interpreted by a magnetomechanical effect generated by the stress field induced by the amorphous tracks in the sample plane which flips the magnetization along the track-axis direction when the stress-induced anisotropy constant surpasses the pristine crystal anisotropy constant at the critical amorphous fraction. In the case of YIG:Si single crystal, a track-induced anisotropy field around 0.1 T is deduced from the Moessbauer spectra under a magnetic field applied in the sample (111) plane which rotates the magnetization back to the easy {l_angle}111{r_angle} magnetization axis lying near the sample (111) plane in a reversible manner. The magnetic ordering of amorphous YIG:Si below 70 K is also studied by Moessbauer spectroscopy under high magnetic field (5 T). A two-dimensional Bruggeman model used for the calculation of the permeability of the crystal+amorphous track composites yields track

  17. Mössbauer and XRD study of hot dip galvanized alloy

    NASA Astrophysics Data System (ADS)

    Kuzmann, E.; Speakman, R.; El-Sharif, M.; Stichleutner, S.; Homonnay, Z.; Klencsár, Z.; Sziráki, L.; Chisholm, C. U.; Lak, Gy. B.

    2016-12-01

    Mössbauer spectroscopy has been used to investigate the nature of the Zinc-Iron alloys present within the Hot Dip Galvanized (HDG) layers of steel with a silicon content of 0.35 %. The investigation also studied the impact of the powder coating pretreatment on the nature of the alloy layers. The acid etching process within the pretreatment process in particular would be expected to have a significant impact on the HDG layer. This study utilized 57Fe Mössbauer spectroscopy to examine identically processed samples prior to and post pre treatment. XRD and 57Fe CEMS measurements were performed on hot galvanized S355J2 + N samples, forming sandwiched structure. Both XRD and CEMS reveal the presence of dominant steel phase in accordance with its estimated occurrence on the surface of the sandwiched samples. Minor Γ-Fe3Zn10, ζ-FeZn15 and solid solution Fe-Zn as well as minor Fe-Si phases could also be identified.

  18. Effect of cycled combustion ageing on a cordierite burner plate

    SciTech Connect

    Garcia, Eugenio

    2010-11-15

    A combination of {sup 57}Fe-Moessbauer spectroscopy and X-ray Powder Diffraction analysis has been employed to study modifications in chemical and mechanical stability occurring in a cordierite burner aged under combustion conditions which simulate the working of domestic boilers. Moessbauer study shows that Fe is distributed into the structural sites of the cordierite lattice as Fe{sup 2+} and Fe{sup 3+} ions located mostly at octahedral sites. Ferric oxide impurities, mainly hematite, are also present in the starting cordierite material accounting for {approx_equal}40% of the total iron phases. From Moessbauer and X-ray diffraction data it can be deduced that, under the combustion conditions used, new crystalline phases were formed, some of the substitutional Fe{sup 3+} ions existing in the cordierite lattice were reduced to Fe{sup 2+}, and ferric oxides underwent a sintering process which results in hematite with higher particle size. All these findings were detected in the burner zone located in the proximity of the flame and were related to possible chemical reactions which might explain the observed deterioration of the burner material. Research Highlights: {yields}Depth profile analyses used as a probe to understand changes in refractory structure. {yields}All changes take place in the uppermost surface of the burner, close to the flame. {yields}Reduction to Fe{sup 2+} of substitutional Fe{sup 3+} ions and partial cordierite decomposition. {yields}Heating-cooling cycling induces a sintering of the existing iron oxide particles. {yields}Chemical changes can explain the alterations observed in the material microstructure.

  19. Influence of Sn{sup 4+} and Sn{sup 4+}/Mg{sup 2+} doping on structural features and visible absorption properties of {alpha}-Fe{sub 2}O{sub 3} hematite

    SciTech Connect

    Gaudon, M.; Pailhe, N.; Majimel, J.; Wattiaux, A.; Abel, J.; Demourgues, A.

    2010-09-15

    Pure, Sn-doped and Mg/Sn co-doped {alpha}-Fe{sub 2}O{sub 3} hematite samples were synthesized by precipitation process. Fe{sub 2}O{sub 3} is the most popular red mineral pigment which is used largely in traditional ceramics, tar and concrete. The compounds were characterized by powder X-ray diffraction (XRD), scanning transmission electronic microscopy (energy dispersive X-ray cartography), Moessbauer spectroscopy, magnetic investigations versus temperature and visible-NIR spectroscopy. Both {sup 57}Fe and {sup 119}Sn Moessbauer analyses combined with rietveld XRD refinements are the ideal techniques to characterize tin-iron oxides. Hence, thanks to these techniques it was shown how the synthesis temperature influences directly the grain size and the dopants concentration limit which can be incorporated into the host hematite matrix. The stabilization of these tetravalent and divalent dopants into the hematite framework leads to reduce the crystal growth and to limit the (AF) ordering due to the formation of cationic vacancies. The study of the Morin magnetic transition emphasizes this demonstration. In a second part, the influence of the dopants incorporation on the material color was investigated in order to show which key parameters allow improving the red color saturation of iron oxides. In order to improve the red color of the hematites, it was shown that the introduction of cationic vacancies-limiting the octahedral distortion thanks to the interruption of the dissymmetric metal-metal orbital coupling-is the key point. Vacancies are created by Sn{sup 4+}, doping for an increase of the introduced Sn{sup 4+} concentration; it acts to the detriment of the color saturation. - Graphical Abstract: Sn-doped or Sn/Mg-doped Fe{sub 2}O{sub 3} hematites, were analyzed by X-ray diffraction refinement, Moessbauer spectroscopy, magnetic characterization and TEM investigations. Their color is correlated to the doping ions concentration.

  20. Field-induced spin reorientation in [Fe/Cr ] n multilayers studied by nuclear resonance reflectivity

    NASA Astrophysics Data System (ADS)

    Andreeva, M.; Gupta, A.; Sharma, G.; Kamali, S.; Okada, K.; Yoda, Y.

    2015-10-01

    We present depth-resolved nuclear resonance reflectivity studies of the magnetization evolution in [57Fe(3nm ) /Cr (1.2 nm ) ] 10 multilayer under applied external field. The measurements have been performed at the station BL09XU of SPring-8 at different values of the external field (0-1500 Oe). We apply the joint fit of the delayed reflectivity curves and the time spectra of the nuclear resonance reflectivity measured at different grazing angles for enhancement of the depth resolution and reliability of results. We show that the azimuth angle, which is used in all papers devoted to the magnetization profile determination, has a more complicated physical sense due to the partially coherent averaging of the scattering amplitudes from magnetic lateral domains. We describe how to select the true azimuth angle from the determined "effective azimuth angle." Finally we obtain the noncollinear twisted magnetization depth profiles where the spin-flop state appears sequentially in different 57Fe layers at increasing applied field.

  1. The Influence of Abrasion on Martian Dust Grains: Evidence from a Study of Antigorite Grains

    NASA Technical Reports Server (NTRS)

    Bishop, Janice L.; Drief, Ahmed; Dyar, M. Darby

    2003-01-01

    Grinding was shown to greatly affect the structure and a number of properties of antigorite grains in a study by Drief and Nieto. Grinding is likely to influence the structure of most clay mineral grains and has been shown recently to influence the structure of kaolinite. The antigorite structure includes curved waves of layered silicate as shown by D dony et al.. Our study was performed in order to characterize in detail changes in the mineral grains resulting from grinding and to assess the influence of physical processes on clay minerals on the surface of Mars. This project includes a combination of SEM, reflectance spectroscopy and Moessbauer spectroscopy.

  2. Mössbauer studies of multiferroics BiFe1 - x Cr x O3 ( x = 0-0.20)

    NASA Astrophysics Data System (ADS)

    Pokatilov, V. S.; Rusakov, V. S.; Sigov, A. S.; Belik, A. A.

    2017-08-01

    The Mössbauer studies on 57Fe nuclei in multiferroics BiFe1 - x Cr x O3 ( x = 0.05, 0.10, and 0.20) have been performed at room temperature. The multiferroics BiFe1 - x Cr x O3 ( x = 0.05, 0.10, and 0.20) with the rhombohedral R3 c structure have been prepared by solid-state synthesis under high pressures. The effect of substitution of Cr cations for Fe cations on the spatial spin-modulated structure, and also hyperfine electrical and magnetic interactions of 57Fe nuclei has been studied. The substituted ferrites demonstrate an anharmonic modulated spin structure of cycloid type, in which iron atoms with different cation environments take part. The anharmonism parameter of the cycloid linearly increases from m = 0.10 at x = 0 to m = 0.78 ± 0.02 at x = 0.20. The constants of magnetic uniaxial anisotropy K u are estimated at room temperature: K u ≈ 0.36 × 106 erg/cm3 at x = 0 and K u ≈ 4.22 × 106 erg/cm3 at x = 0.20.

  3. Cation distribution in Ni–Cu–Zn nanoferrites from {sup 57}Fe in-field Mössbauer spectra

    SciTech Connect

    Prameela, P.; Kumar, A. Mahesh; Choudary, G.S.V.R.K.; Rao, K.H.; Reddy, V.R.

    2014-11-15

    Highlights: • Occupancy of copper ions at about 20% towards tetrahedral sites. • Distribution is proposed on the basis of % of Fe ions at both A and B sites. • Distribution is checked by estimating the theoretical lattice constant values. - Abstract: The nanoparticles of Ni{sub 1−x}Cu{sub x}Zn{sub 0.35}Fe{sub 2}O{sub 4} were synthesized by sol–gel method using polyvinyl alcohol as a chelating agent. X-ray diffraction patterns of all the samples confirmed the single phase spinel structure. The site occupancy of copper in the nanosized nickel–zinc ferrite spinels was investigated with the help of in-field Mössbauer spectroscopy. Cation distribution for the whole series of compositions was proposed by considering the amounts of iron ions present at both tetrahedral and octahedral interstitial sites in the spinel lattice. Confirmation of the proposed distributions was done by estimating quantitatively the lattice parameters for these compositions and comparing their values with those of the experimentally observed ones.

  4. Resonant nuclear scattering of synchrotron radiation: Detector development and specular scattering from a thin layer of {sup 57}Fe

    SciTech Connect

    Baron, A.Q.R.

    1995-04-01

    This thesis explores resonant nudear scattering of synchrotron radiation. An introductory chapter describes some useful concepts, such as speedup and coherent enhancement, in the context of some basic physical principles. Methods of producing highly monochromatic synchrotron beams usmg either electronic or nuclear scattering are also discussed. The body of the thesis concentrates on detector development and specular scattering from iynthetic layered materials. A detector employing n-dcrochannel plate electron multipliers is shown to have good ({approximately}50%) effidency for detecting 14.4 key x-rays incident at small ({approximately}0.5 degree) grazing angles onto Au or CsI photocathodes. However, being complicated to use, it was replaced with a large area (>=lan2) avalanche photodiode (APD) detector. The APD`s are simpler to use and have comparable (30--70%) efficiencies at 14.4 key, subnanosecond time resolution, large dynan-dc range (usable at rates up to {approximately}10{sup 8} photons/second) and low (<{approximately}0.01 cts/sec) background rates. Maxwell`s equations are used to derive the specular x-ray reflectivity of layered materials with resonant transitions and complex polarization dependencies. The effects of interfadal roughness are treated with some care, and the distorted wave Born approximation (DWBA) used to describe electronic scattering is generalized to the nuclear case. The implications of the theory are discussed in the context of grazing incidence measurements with emphasis on the kinematic and dynamical aspects of the scattering.

  5. The Study of ( n,d) Reaction Cross Sections for Some Medium Weight Targets up to 30 MeV

    NASA Astrophysics Data System (ADS)

    Aydin, A.; Şahan, M.; Tel, E.; Şahan, H.; Uğur, F. A.

    2011-08-01

    In this study, neutron incident reaction cross sections for some medium target nuclei ( 44 Ca, 65 Cu, 54 Fe, 56 Fe, 57 Fe, 58 Ni, 60 Ni and 67 Zn) have been investigated for the ( n,d) reaction cross sections. These new calculations on the excitation functions of 44 Ca(n,d) 43 K, 65 Cu(n,d) 44 Ni, 54 Fe(n,d) 53 Mn, 56 Fe(n,d) 55 Mn, 57 Fe(n,d) 56 Mn, 58 Ni(n,d) 57 Co, 60 Ni(n,d) 59 Co and 67 Zn(n,d) 66 Cu reactions have been carried out up to 30 MeV incident neutron energy. In these calculations, the pre-equilibrium and equilibrium effects have been investigated. The PEQ calculations involve the new evaluated the Geometry Dependent Hybrid model. Equilibrium effects are calculated according to the Weisskopf-Ewing model. By using the new cross sections formulae for ( n,d) reactions developed by Aydin et al., the obtained results have been discussed and compared with the available experimental data taken from EXFOR database.

  6. The Mössbauer Parameters of the Proximal Cluster of Membrane-Bound Hydrogenase Revisited: A Density Functional Theory Study

    PubMed Central

    2015-01-01

    An unprecedented [4Fe-3S] cluster proximal to the regular [NiFe] active site has recently been found to be responsible for the ability of membrane-bound hydrogenases (MBHs) to oxidize dihydrogen in the presence of ambient levels of oxygen. Starting from proximal cluster models of a recent DFT study on the redox-dependent structural transformation of the [4Fe-3S] cluster, 57Fe Mössbauer parameters (electric field gradients, isomer shifts, and nuclear hyperfine couplings) were calculated using DFT. Our results revise the previously reported correspondence of Mössbauer signals and iron centers in the [4Fe-3S]3+ reduced-state proximal cluster. Similar conflicting assignments are also resolved for the [4Fe-3S]5+ superoxidized state with particular regard to spin-coupling in the broken-symmetry DFT calculations. Calculated 57Fe hyperfine coupling (HFC) tensors expose discrepancies in the experimental set of HFC tensors and substantiate the need for additional experimental work on the magnetic properties of the MBH proximal cluster in its reduced and superoxidized redox states. PMID:26598030

  7. Mössbauer effect studies on organometallic237Np-compounds

    NASA Astrophysics Data System (ADS)

    Adrian, G.; Appel, H.; Bohlander, R.; Haffner, H.; Kanellakopulos, B.

    1988-02-01

    A series of organometallic compounds of tetravalent Neptunium was studied by Moessbauer methods. Three of them will be presented here. Their molecular structure is close to C3v symmetry. The data were parameterised on the basis of an anisotropic paramagnetic relaxation model and will be interpreted for each individual compound. In general it can be stated that distortions from axially symmetric hyperfine parameters were observed, no magnetic ordering occured at all temperatures above 1.5 K and anisotropic relaxation frequencies had to be introduced to fit the spectra.

  8. 5 7 Fe Emission Mössbauer Study on Gd 3 Ga 5 O 1 2 implanted with dilute 5 7 Mn

    NASA Astrophysics Data System (ADS)

    Krastev, P. B.; Gunnlaugsson, H. P.; Nomura, K.; Adoons, V.; Gerami, A. M.; Johnston, K.; Ncube, M.; Mantovan, R.; Masenda, H.; Matveyev, Y. A.; Mølholt, T. E.; Unzueta, I.; Bharuth-Ram, K.; Gislason, H.; Langouche, G.; Naidoo, D.; Ólafsson, S.

    2016-12-01

    57Fe emission Mössbauer spectroscopy has been applied to study the lattice location and properties of Fe in gadolinium gallium garnet Gd3Ga5 O 12 (GGG) single crystals in the temperature interval 300 - 563 K within the extremely dilute (<10-4 at.%) regime following the implantation of57Mn ( T 1 / 2= 1.5 min.) at ISOLDE/CERN. These results are compared with earlier Mössbauer spectroscopy study of Fe-doped gadolinium gallium garnet Gd3Ga5 O 12(GGG), with implantation fluences between 8×1015 and 6×1016 atoms cm-2. Three Fe components are observed in the emission Mössbauer spectra: (i) high spin Fe2+ located at damage sites due to the implantation process, (ii) high spin Fe3+ at substitutional tetrahedral Ga sites, and (iii) interstitial Fe, probably due to the recoil imparted on the daughter57∗Fe nucleus in the β - decay of57Mn. In contrast to high fluence57Fe implantation studies the Fe3+ ions are found to prefer the tetrahedral Ga site over the octahedral Ga site. No annealing stages are evident in the temperature range investigated. Despite the very low concentration, high-spin Fe3+ shows fast spin relaxation, presumably due to an indirect interaction between nearby gadolinium atoms.

  9. A computer program for Moessbauer data processing

    NASA Technical Reports Server (NTRS)

    Howser, L. M.; Singh, J. J.; Smith, R. E., Jr.

    1972-01-01

    A computer program to analyze Mossbauer data is presented in detail. The least-squares curve fitting techniques described apply to single line spectra, single hyperfine spectra, or when the constituent spectra are separated well enough to let the individual absorption peaks stand alone. The present program is not adapted for complex spectra resulting from the existence of several local environments in the absorber iron alloy. Sample problems are presented to aid the user in setting up and running the program. The program is written in FORTRAN 4 language for the Control Data 6000 series digital computer with the SCOPE 3.0 operating system and requires approximately 115,000 octal locations of core storage. A typical case with one absorption peak runs in 20 seconds, and a typical problem with six absorption peaks requires 50 seconds.

  10. Moessbauer spectroscopy of the SNC meteorite Zagami

    NASA Technical Reports Server (NTRS)

    Agerkvist, D. P.; Vistisen, L.

    1993-01-01

    We have performed Mossbauer spectroscopy on two different pieces of the meteorite Zagami belonging to the group of SNC meteorites. In one of the samples we found a substantial amount of olivine inter grown with one kind of pyroxene, and also another kind of pyroxene very similar to the pyroxene in the other sample we examined. Both samples showed less than 1 percent of Fe(3+) in the silicate phase. The group of SNC meteorites called shergottites, to which Zagami belongs, are achondrites whose texture, mineralogy and composition resembles those of terrestrial diabases. The results from the investigation are presented.

  11. Moessbauer mineralogy of calcined Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Morris, Richard V.; Zolensky, M. E.; Hiroi, T.; Lipschutz, M. E.

    1994-01-01

    The three Antarctic meteorites B7904, Y82162, and Y86720 are unusual because they have characteristics in common with both CI and CM groups and because they apparently underwent thermal alteration after hydrous alteration on their parent body. They are also spectrally similar (visible and near-IR) to C, G, B, and F asteroids, which may imply that the surface materials on those asteroids may have undergone thermal alteration. Based on the reflectance spectra of samples of Murchison (CM2 carbonaceous chondrite) that were thermally altered in the laboratory (cryopumped and initial 10(exp -5) atm H2), Hiroi et al. concluded that putative thermal alteration occurred at temperatures of 600 to 1000 C. Similar experiments have been done on Murchison and reported mineralogical changes based on data from transmission electron diffraction microscopy, electron diffraction, and analytical electron microscopy. We report here the Mossbauer mineralogy of the same samples of thermally-altered Murchison. Mossbauer mineralogy gives the molar distribution of Fe among its oxidation states and iron-bearing mineralogies.

  12. Role of iron in Na 1.5Fe 0.5Ti 1.5(PO 4) 3/C as electrode material for Na-ion batteries studied by operando Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Difi, Siham; Saadoune, Ismael; Sougrati, Moulay Tahar; Hakkou, Rachid; Edstrom, Kristina; Lippens, Pierre-Emmanuel

    2016-12-01

    The role of iron in Na 1.5Fe 0.5Ti 1.5(PO 4)3/C electrode material for Na batteries has been studied by 57Fe Mössbauer spectroscopy in operando mode. The potential profile obtained in the galvanostatic regime shows three plateaus at different voltages due to different reaction mechanisms. Two of them, at 2.2 and 0.3 V vs Na +/Na 0, have been associated to redox processes involving iron and titanium in Na 1.5Fe 0.5Ti 1.5(PO 4)3. The role of titanium was previously elucidated for NaTi 2(PO 4)3 and the effect of the substitution of Fe for Ti was investigated with 57Fe Mössbauer spectroscopy. We show that iron is an electrochemically active center at 2.2 V with the reversible Fe 3+/Fe 2+ transformation and then remains at the oxidation state Fe 2+ along the sodiation until the end of discharge at 0 V.

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

    SciTech Connect

    Panda, Alaka; Singh, L. Herojit; Rajagopalan, S.; Govindaraj, R. Ramachandran, Renjith; Kalavathi, S.; Amarendra, G.

    2016-05-23

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

  14. Mössbauer study of cobalt and iron in the cyanobacterium (blue green alga)

    NASA Astrophysics Data System (ADS)

    Ambe, Shizuko

    1990-07-01

    Mössbauer emission and absorption studies have been performed on cobalt and iron in the cyanobacterium (blue-green alga). The Mössbauer spectrum of the cyanobacterium cultivated with57Co is decomposed into two doublets. The parameters of the major doublet are in good agreement with those of cyanocobalamin (vitamin B12) labeled with57Co. The other minor doublet has parameters close to those of Fe(II) coordinated with six nitrogen atoms. These suggest that cobalt is used for the biosynthesis of vitamin B12 or its analogs in the cyanobacterium. The spectra of the cyanobacterium grown with57Fe show that iron is in the high-spin trivalent state and possibly in the form of ferritin, iron storage protein.

  15. Mössbauer studies of impactites from Huamalies province in Huanuco Region

    NASA Astrophysics Data System (ADS)

    Bustamante, A.; Espinoza, S.; Morales, G.; Scorzelli, R. B.

    2005-11-01

    This report is about the X-ray diffraction and Mössbauer studies of three impactite samples denominated PMe-8, PMe-9 and PMe-11 from Huamalies Province in Huánuco Region, Peru. When terrestrial rocks are submitted to pressures higher than 60 GP, the majority is completely melted, forming a kind of glass called impactites. X-ray diffraction indicates the presence of quartz as the principal mineralogical phase in all samples. The 57Fe Mössbauer spectra at room temperature of samples PMe-8 and PMe-9 show broadened spectra that were fitted using a distribution model. The most probable field of the magnetic component is 34 T, corresponding to the presence of small particles of goethite, confirmed by the 4.2 K spectrum. For the sample PMe-11, the MS showed the presence of well crystallized hematite.

  16. Mössbauer study of Fe-Re alloys prepared by mechanical alloying

    NASA Astrophysics Data System (ADS)

    Konieczny, R.; Idczak, R.

    2016-12-01

    The room temperature Mössbauer spectra of 57Fe were measured for nanocrystalline iron-based solid solutions Fe 1- x Re x , prepared by mechanical alloying with x in the range 0.01 ≤ x ≤ 0.04. The obtained data were analysed in terms of the binding energy E b between two rhenium atoms in the Fe-Re system. The extrapolated value of E b for x = 0 was used for computation of enthalpy of solution of rhenium in iron. The result was compared with that resulting from the cellular atomic model of alloys by Miedema as well as with value, derived from proper data for Fe-Re solid solutions obtained by melting in an arc furnace. From the comparison it follows that our findings are in agreement with the Miedema's model predictions and previous Mössbauer studies.

  17. Fe-doping and strain effects on structural and magnetotransport properties in La{sub 2/3}Ca{sub 1/3}Mn{sub 1-y}Fe{sub y}O{sub 3} thin films.

    SciTech Connect

    Arnache, O; Girata, D.; Hoffmann, A.; Materials Science Division; Univ. Antioquia

    2008-01-01

    The influence of {sup 57}Fe-doping and strain effects on the structural and magnetotransport properties of undoped and lightly doped {sup 57}Fe (1 and 3% at Mn site) La{sub 2/3}Ca{sub 1/3}MnO{sub 3} thin films and bulk powder samples have been studied. Thin films were grown on (100)-SrTiO{sub 3} (STO) and (100)-LaAlO{sub 3} (LAO) single crystal substrates, via high O{sub 2} pressure (500 mTorr) using dc magnetron sputtering. Conversion electron Moessbauer (CEM) spectra measured at room temperature in the paramagnetic regime of the Fe-doped samples do not show significant differences in the isomeric shift for the case of the La{sub 2/3}Ca{sub 1/3}MnO{sub 3} films doped with 1 and 3% iron. The isomeric shift values correspond to the presence of Fe in the 3+ state with octahedral coordination, thus indicating that Fe is incorporated into the structure by substituting Mn. The absence of further states in the spectra indicates that Fe is not involved in forming other additional impurity phases. The x-ray {theta}-2{theta} scan showed that all thin films on LAO and STO have single phase and c-axis strong orientation along the growth direction and the Fe doping gives rise to a relaxation of the epitaxial strain. Finally, we have observed that the saturation magnetization, Curie temperature, metal-insulator transition, and magnetoresistance vary nonmonotonically with increased Fe concentration. This behavior can be understood in terms of competing influences from the strain relaxation, which enhances the tendency to order ferromagnetically, and the reduced double exchange, which is detrimental to the ferromagnetic order.

  18. Nuclear forward scattering vs. conventional Mossbauer studies of atomically tailored Eu-based materials.

    SciTech Connect

    Konjhodzic, A.; Adamczyk, A.; Hasan, Z.; Alp, E. E.; Sturhahn, W.; Zhao, J.; Carroll, J. J.; Vagizov, F.; Univ. of Philadelphia; Youngstown State Univ.

    2006-01-01

    With the decrease in size of devices, rapid characterization of nano-devices is an inevitable necessity. It is shown that Moessbauer spectroscopy using synchrotron radiation from the advanced photon source provides such a tool of investigation. Results are presented and compared for conventional Moessbauer and Nuclear Forward Scattering for {sup 151}Eu-doped magnesium sulfide as an example, especially at low concentrations.

  19. Coexistence of ferromagnetism and superconductivity: magnetization and Mössbauer studies of EuFe₂(As₁ - xPx)₂.

    PubMed

    Nowik, I; Felner, I; Ren, Z; Cao, G H; Xu, Z A

    2011-02-16

    Magnetization and (57)Fe and (151)Eu Mössbauer studies of EuFe(2)(As(1 - x)P(x))(2) (x = 0-1.0) at temperatures (5-300 K) have been performed. The magnetization studies show a decrease of the divalent Eu sublattice antiferromagnetic transition temperature from T(AFM) = 20 K for x = 0 to 16 K at x≈0.2. For x > 0.2, the Eu sublattice is ferromagnetically ordered at T(FM), which increases up to 27 K for x = 1.0. For 0.2 < x < 0.5, the system becomes superconducting. (151)Eu Mössbauer studies in the antiferromagnetic range show a constant saturation hyperfine field of 26.2 T and that the magnetization is almost perpendicular to the c-axis. On the other hand, in the ferromagnetic range, the hyperfine field increases up to 30.8 T (for x = 1) and the easy axis is almost parallel to the c-axis. In both regions the magnetic axis seems to be tilted from the basal plane or the c-axis by ∼ 20°. The (57)Fe Mössbauer studies show no magnetism in the iron site for x > 0.2, yet at 5 K exhibit transferred magnetic hyperfine fields (∼1 T) from the ferromagnetically ordered Eu sublattice, even in the superconducting region. Superconductivity in the presence of ferromagnetism is generally not observable. However, transferred magnetic hyperfine fields in the superconducting state are observed here for the first time.

  20. Emission Mössbauer spectroscopy study of fluence dependence of paramagnetic relaxation in Mn/Fe implanted ZnO

    NASA Astrophysics Data System (ADS)

    Masenda, H.; Geburt, S.; Bharuth-Ram, K.; Naidoo, D.; Gunnlaugsson, H. P.; Johnston, K.; Mantovan, R.; Mølholt, T. E.; Ncube, M.; Shayestehaminzadeh, S.; Gislason, H. P.; Langouche, G.; Ólafsson, S.; Ronning, C.

    2016-12-01

    Emission Mössbauer Spectroscopy following the implantation of radioactive precursor isotope 57Mn+ ( T 1/2= 1.5 min) into ZnO single crystals at ISOLDE/CERN shows that a large fraction of 57Fe atoms produced in the 57Mn beta decay is created as paramagnetic Fe3+ with relatively long spin-lattice relaxation times. Here we report on ZnO pre-implanted with 56Fe to fluences of 2×1013, 5×10 13 and 8 × 1013 ions/cm2 in order to investigate the dependence of the paramagnetic relaxation rate of Fe3+ on fluence. The spectra are dominated by magnetic features displaying paramagnetic relaxation effects. The extracted spin-lattice relaxation rates show a slight increase with increasing ion fluence at corresponding temperatures and the area fraction of Fe3+ at room temperature reaches a maximum contribution of 80(3)% in the studied fluence range.

  1. Comparative study of Aliskerovo, Anyujskij, Sikhote-Alin and Sterlitamak iron meteorites using Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Goryunov, M. V.; Oshtrakh, M. I.; Chukin, A. V.; Grokhovsky, V. I.; Semionkin, V. A.

    2016-12-01

    A comparative study of Sikhote-Alin IIAB, Anyujskij IIAB, Aliskerovo IIIE-an and Sterlitamak IIIAB iron meteorites was carried out using Mössbauer spectroscopy with a high velocity resolution as well as using metallography, scanning electron microscopy with energy dispersive spectroscopy and X-ray diffraction. Different numbers of spectral components were found in the Mössbauer spectra of Sikhote-Alin IIAB and Anyujskij IIAB and in the spectra of Aliskerovo IIIE-an and Sterlitamak IIIAB iron meteorites. The values of hyperfine field at the 57Fe nuclei obtained for spectral components were related to α-Fe(Ni, Co), α 2-Fe(Ni, Co) and γ-Fe(Ni, Co) phases with variations in Ni concentration.

  2. Fe-57 Mössbauer Study of the Murrili Ordinary Chondrite

    NASA Astrophysics Data System (ADS)

    Cadogan, J. M.; Bland, P. A.; Benedix, G. K.; Towner, M. C.; Sansom, E. K.; Devillepoix, H.; Howie, R. M.; Paxman, J. P.; Cupak, M.; Cox, M. A.; Jansen-Sturgeon, T.; Stuart, D.; Strangway, D.

    2016-08-01

    The Murrili meteorite fell in Lake Eyre South, South Australia, after being imaged and located by the Desert Fireball Network. It displays an unusual heterogeneous weathering throughout the stone, here quantified using 57Fe Mössbauer spectroscopy.

  3. Mössbauer study of the effect of pH on Fe valence in iron-polygalacturonate as a medicine for human anaemia

    NASA Astrophysics Data System (ADS)

    Kuzmann, E.; Garg, V. K.; de Oliveira, A. C.; Klencsár, Z.; Szentmihályi, K.; Fodor, J.; May, Z.; Homonnay, Z.

    2015-02-01

    Iron-polygalacturonate complexes have been synthesized from polygalacturonic acid by applying a novel preparation method in order to develop medicine suitable for the effective iron supplementation of the human body in the case of anemia. Since the iron uptake depends on the oxidation state of iron, 57Fe Mössbauer spectroscopy was used to study the occurrence of different valence states in the iron-polygalacturonate complexes prepared under different circumstances. The Mössbauer-spectra indicated the presence of iron both in FeII and FeIII states in the investigated iron-polygalacturonate compounds, the occurrence of which varied with the preparation parameters. A correlation of the relative occurrence of iron valence states with the pH has been found. The relative occurrence of FeIII was found to increase with increasing pH. The knowledge of this correlation can help find optimum preparation conditions of iron-polygalacturonates to cure human anemia.

  4. Magnetic measurements of the transuranium elements and charge state characterization of actinides in monazite. Progress report

    SciTech Connect

    Huray, P. G.

    1980-01-01

    A micromagnetic susceptometer for the purpose of measuring extremely small sample quantities (on the microgram level) was designed, constructed, and calibrated in previous years. (The 1979 progress report gives details of its operation.) This device has operated without significant downtime in this funding period, and much progress has been made in the magnetic characterization of elements beyond Am in the periodic table. This program has roughly doubled man's knowledge of magnetism in Cm, Bk, and Cf, and includes the only Es magnetic measurements to date. The incorporation of an automatic data collection system in this period has made analysis much more accurate, and has allowed quicker turnaround of compounds and metals for study. Results obtained for the compounds and metals studied this year are summarized. The lanthanide orthophosphates are being investigated as an alternate means of primary containment for high-level actinide wastes. Researchers at the Oak Ridge National Laboratory are involved in preparation of actinide-doped compounds for all of the lanthanide transition series (La through Lu) for a study of leaching characteristics and E.S.R. classification. To aid this study the charge state of /sup 237/Np or /sup 57/Fe has been identified, either in the as-prepared compounds or following radioactive decay of /sup 241/Am via the Moessbauer Effect. The final charge state will be an influential variable in the immobilization characteristics of the waste products stored in this synthetic monazite form. 10 figures, 1 table. (RWR)

  5. NiO/Fe(001): Magnetic anisotropy, exchange bias, and interface structure

    SciTech Connect

    Mlynczak, E.; Luches, P.

    2013-06-21

    The magnetic and structural properties of NiO/Fe epitaxial bilayers grown on MgO(001) were studied using magnetooptic Kerr effect (MOKE) and conversion electron Moessbauer spectroscopy (CEMS). The bilayers were prepared under ultra high vacuum conditions using molecular beam epitaxy with oblique deposition. Two systems were compared: one showing the exchange bias (100ML-NiO/24ML-Fe), ML stands for a monolayer, and another where the exchange bias was not observed (50ML-NiO/50ML-Fe). For both, the magnetic anisotropy was found to be complex, yet dominated by the growth-induced uniaxial anisotropy. The training effect was observed for the 100ML-NiO/24ML-Fe system and quantitatively described using the spin glass model. The composition and magnetic state of the interfacial Fe layers were studied using {sup 57}Fe-CEMS. An iron oxide phase (Fe{sup 3+}{sub 4}Fe{sup 2+}{sub 1}O{sub 7}), as thick as 31 A, was identified at the NiO/Fe interface in the as-deposited samples. The ferrimagnetic nature of the interfacial iron oxide film explains the complex magnetic anisotropy observed in the samples.

  6. The efficacy of a local ascorbic acid-rich food in improving iron absorption from Mexican diets: a field study using stable isotopes.

    PubMed

    Diaz, Margarita; Rosado, Jorge L; Allen, Lindsay H; Abrams, Steve; García, Olga P

    2003-09-01

    One potentially sustainable approach to improving iron status at the community level is to encourage the consumption of local ascorbic acid-rich foods, in conjunction with meals high in nonheme iron. The study, conducted in rural Mexico, measured stable isotopes of iron to evaluate the effect on iron absorption of the addition of 25 mg ascorbic acid as agua de limón (limeade) to 2 typical meals per day for 2 wk. Fifteen nonpregnant, nonlactating, iron-deficient (ferritin < 12 microg/L) women (x +/- SD age: 28.3 +/- 7.7 y) fasted overnight and were brought to a community clinic. After an initial blood sample, subjects consumed 0.25 mg (57)Fe with both breakfast and lunch for 14 d. On day 29, another blood sample was taken, and a reference dose of 2.7 mg (58)Fe with 25 mg ascorbic acid was given. For the following 15 d, participants consumed 0.25 mg (57)Fe added to both breakfast and lunch with 25 mg ascorbic acid added to each meal as limeade. A final blood sample was taken on day 59. Iron absorption was calculated from recovery of isotopes in blood obtained 14 d after administration of each isotope. When 25 mg ascorbic acid as limeade was added to test meals twice a day for 2 wk, iron absorption increased significantly (P < 0.001) in every subject: the mean absorption rose from 6.6 +/- 3.0% to 22.9 +/- 12.6%. The consumption of 25 mg ascorbic acid as limeade twice daily with meals substantially improved iron absorption and may improve the iron status of nonpregnant, nonlactating, iron-deficient women.

  7. Study of the surface chemistry and morphology of single walled carbon nanotube-magnetite composites

    SciTech Connect

    Marquez-Linares, F.; Uwakweh, O.N.C.; Lopez, N.; Chavez, E.; Polanco, R.; Morant, C.; Sanz, J.M.; Elizalde, E.; Neira, C.; Nieto, S.; Roque-Malherbe, R.

    2011-03-15

    The study of the morphologies of the single walled carbon nanotube (SWCNT), magnetite nanoparticles (MNP), and the composite based on them was carried with combined X-ray diffraction (XRD), Raman spectroscopy (RS), scanning electron microscopy (SEM), field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). These techniques together with thermogravimetric analyses (TGA) and diffuse reflectance infrared transform spectroscopy (DRIFTS) confirmed the production of pure single phases, and that the composite material consisted of MNP attached to the outer surface of the SWCNT. The Moessbauer spectroscopy (MS) research showed the presence of a large quantity of Lewis acid sites in the highly dispersed magnetite particles supported on the SWCNT outer surface. The DRIFTS carbon dioxide adsorption study of the composites revealed significant adsorption of carbon dioxide, fundamentally in the Lewis acid sites. Then, the Lewis acid sites were observed to be catalytically active. Further, the electron exchange between the Lewis acid sites and the basic or amphoteric adsorbed molecules could influence the magnetic properties of the magnetite. Consequently, together with this first ever use of MS in the study of Lewis acid sites, this investigation revealed the potential of the composites for catalytic and sensors applications. -- Graphical abstract: A large amount of Lewis acid sites were found in the highly dispersed magnetite which is supported on the SWCNT outer surface. Display Omitted Research highlights: {yields} The obtained materials were completely characterized with XRD, Raman and SEM-TEM. {yields} DRIFT, TGA and adsorption of the composites allowed understand the material formation. {yields} This is the first report of a study of Lewis sites by Moessbauer spectroscopy.

  8. Coexistence of magnetic fluctuations and superconductivity in SmFe0.95Co0.05AsO seen in 57Fe Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Long, G.; Demarco, M.; Chudyk, M.; Steiner, J.; Coffey, D.; Zeng, H.; Li, Y. K.; Cao, G. H.; Xu, Z. A.

    2011-08-01

    The Mössbauer spectra (MS) of powder samples of SmFe1-xCoxAsO (x = 0.0, 0.05, and 0.1) were measured in applied fields up to 9 T and at temperatures up to 298 K. SmFeAsO is magnetically ordered with TN = 137 K and has a hyperfine magnetic field of (4.98 ± 0.18) T at 4.2 K. In applied magnetic fields, the MS is consistent with a distribution of hyperfine magnetic fields of width Happlied+Hhyperfine. This arises because the angles between the direction of the ordered field in the crystallites making up the sample are randomly distributed about the direction of the applied field. The MS of the superconductors SmFe0.95Co0.05AsO (TC≃5 K) and SmFe0.9Co0.1AsO (TC≃17 K) are well described by a single peak from room temperature to 4.2 K indicating the absence of static magnetic order. However, the half width at half maximum, Γ, of the peak in SmFe0.95Co0.05AsO increases with decreasing temperature from its high temperature value, 0.13 mm/s at 25 K, to 0.25 mm/s at 10 K. No such temperature dependence is seen in SmFe0.9Co0.1AsO. We analyze this temperature dependence in terms of a fluctuating hyperfine magnetic field model whose frequency at 4.2 K is found to be ˜5-10 MHz, giving direct evidence of coexisting magnetic fluctuations and superconductivity at the interface in the phase diagram between the regions with magnetic and superconducting order. In a 5 T applied field, SmFe0.95Co0.05AsO is no longer superconducting; however, the temperature-dependent fluctuating magnetic field is still present and largely unchanged. The absence of fluctuations in superconducting SmFe0.9Co0.1AsO and their presence in superconducting SmFe0.95Co0.05AsO in zero applied field and in nonsuperconducting SmFe0.95Co0.05AsO at 5 T suggests that magnetic order is in competition with superconductivity in SmFe1-xCoxAsO.

  9. Comment on "Calibration of (57)Fe Mössbauer constants by first principles" Phys. Chem. Chem. Phys., 2016, 18, 10201-10206.

    PubMed

    Grandjean, Fernande; Long, Gary J

    2016-09-21

    The proportionality constant, α, between the observed isomer shifts and the calculated electron probability density at the iron nucleus has been reevaluated in terms of the correct experimental isomer shifts relative to α-iron and their corresponding accuracy, which should be considered in the linear regression fit yielding α. The iron-57 excited state nuclear quadrupole moment, Q, is not a "relative" value and its widely accepted experimental value is 0.16(1) × 10(-28) m(2) as also confirmed by nuclear model calculations.

  10. 57Fe Mössbauer spectroscopy and magnetization of cation deficient Fe2TiO4 and FeCr2O4. Part II: Magnetization data

    NASA Astrophysics Data System (ADS)

    Schmidbauer, E.

    1987-12-01

    Magnetic properties are reported for synthetic cation deficient Fe2TiO4 and FeCr2O4 particles (<1 μm). Cation deficiency, achieved by oxidation, is characterized by the oxidation parameter z which represents the fraction of Fe2+ ions converted to Fe3+ in the spinel lattice (0≤ z≤1). Fe2TiO4 ( z=0.85) has a Curie temperature T c that can only approximately be given with a value in the range 400 700 K and it has a magnetic moment per formula unit M≈0.50 μB (μB=Bohr's magneton) at 4.2 K, for FeCr2O4 it is T c≥520 K and M (4.2 K) ≈0.16 μB. Magnetic hysteresis parameters at various temperatures show in part characteristic features due to relaxation phenomena. In the Ti-spinel, the latter are caused by a superposition of superparamagnetism and spin relaxation and in the Cr-spinel by superparamagnetism, in agreement with Mössbauer data (part I of this paper). The cation and vacancy distribution and magnetic coupling are discussed in both compositions with respect to magnetic moment data considering magnetic dilution by incorporated vacancies, and in the Ti-spinel also by non magnetic Ti4+.

  11. Nuclear resonant x-ray spectroscopy of (Mg,Fe)SiO{sub 3} orthoenstatites.

    SciTech Connect

    Jackson, J. M.; Hamecher, E. A.; Sturhahn, W.; X-Ray Science Division; California Inst. of Tech.

    2009-05-01

    We present nuclear resonant inelastic X-ray scattering (NRIXS) and synchrotron Moessbauer spectroscopy (SMS) measurements, both nuclear resonant X-ray spectroscopic methods, on synthetic samples of orthoenstatite-structured (Mg,{sup 57}Fe)SiO{sub 3}, a representative component in Earth's upper mantle. All measurements were performed at ambient conditions. NRIXS spectra were measured for three samples of orthoenstatite containing 20, 13, and 7 mol% FeSiO{sub 3}. The Debye sound velocities were determined from the low-energy region of the partial phonon density of states (PDOS). With known density and bulk modulus, the shear modulus, compressional and shear wave velocities have been computed. The sound velocities obtained from NRIXS are in good agreement with sound velocities obtained using Brillouin spectroscopy and ultrasonic methods for similar compositions. An important advantage of NRIXS is access to additional thermodynamic information, such as the average force constant, mean-square displacement, obtained from the PDOS. We discuss the contribution of the vibrational spectra to these quantities. In addition to the PDOS, the electronic environment of the iron sites in (Mg{sub 0.87}{sup 57}Fe{sub 0.13})SiO{sub 3} orthoenstatite was determined using {sup 57}Fe SMS and conventional Moessbauer spectroscopy. Evaluation of the Moessbauer spectra reveals two distinct iron sites, which are well distinguished by their hyperfine fields. The minority and majority sites are consistent with high-spin Fe{sup 2+} in the M1 and M2 sites, respectively.

  12. Iron Bioavailability from Ferric Pyrophosphate in Extruded Rice Cofortified with Zinc Sulfate Is Greater than When Cofortified with Zinc Oxide in a Human Stable Isotope Study.

    PubMed

    Hackl, Laura; Zimmermann, Michael B; Zeder, Christophe; Parker, Megan; Johns, Paul W; Hurrell, Richard F; Moretti, Diego

    2017-03-01

    Background: Extruded rice grains are often cofortified with iron and zinc. However, it is uncertain if the addition of zinc to iron-fortified rice affects iron absorption and whether this is zinc-compound specific.Objective: We investigated whether zinc, added as zinc oxide (ZnO) or zinc sulfate (ZnSO4), affects human iron absorption from extruded rice fortified with ferric pyrophosphate (FePP).Methods: In 19 iron-depleted Swiss women (plasma ferritin ≤16.5 μ/L) aged between 20 and 39 y with a normal body mass index (in kg/m(2); 18.7-24.8), we compared iron absorption from 4 meals containing fortified extruded rice with 4 mg Fe and 3 mg Zn. Three of the meals contained extruded rice labeled with FePP ((57)FePP): 1) 1 meal without added zinc ((57)FePP-Zn), 2) 1 cofortified with ZnO ((57)FePP+ZnO), and 3) 1 cofortified with ZnSO4 ((57)FePP+ZnSO4). The fourth meal contained extruded rice without iron or zinc, extrinsically labeled with ferrous sulfate ((58)FeSO4) added as a solution after cooking. All 4 meals contained citric acid. Iron bioavailability was measured by isotopic iron ratios in red blood cells. We also measured relative in vitro iron solubility from (57)FePP-Zn, (57)FePP+ZnO, and (57)FePP+ZnSO4 expressed as a fraction of FeSO4 solubility.Results: Geometric mean fractional iron absorption (95% CI) from (57)FePP+ZnSO4 was 4.5% (3.4%, 5.8%) and differed from (57)FePP+ZnO (2.7%; 1.8%, 4.1%) (P < 0.03); both did not differ from (57)FePP-Zn: 4.0% (2.8%, 5.6%). Relative iron bioavailabilities compared with (58)FeSO4 were 62%, 57%, and 38% from (57)FePP+ZnSO4, (57)FePP-Zn, and (57)FePP+ZnO, respectively. In vitro solubility from (57)FePP+ZnSO4 differed from that of (57)FePP-Zn (14.3%; P < 0.02) but not from that of (57)FePP+ZnO (10.2% compared with 13.1%; P = 0.08).Conclusions: In iron-depleted women, iron absorption from FePP-fortified extruded rice cofortified with ZnSO4 was 1.6-fold (95% CI: 1.4-, 1.9-fold) that of rice cofortified with ZnO. These findings

  13. Techniques for inelastic x-ray scattering with {mu}eV resolution.

    SciTech Connect

    Rohlsberger, R.

    1998-10-23

    We introduce a novel type of spectrometer that provides a {micro}eV bandpass together with a tunability over a few meV. The technique relies on nuclear resonant scattering (Moessbauer effect) of synchrotrons radiation at the 14.4-keV resonance of {sup 57}Fe. Energy tuning is achieved by the Doppler effect in high speed rotary motion. The resonantly scattered monochromatic radiation is extracted by a polarization filtering technique or by spatial separation due to the ''nuclear lighthouse effect''.

  14. Neutron study of magnetic excitations in 8-nm {alpha}-Fe{sub 2}O{sub 3} nanoparticles

    SciTech Connect

    Theil Kuhn, L.; Lefmann, K.; Bahl, C. R. H.; Ancona, S. Nyborg; LindgA rd, P.-A.; Frandsen, C.; Madsen, D. E.; Moerup, S.

    2006-11-01

    By use of inelastic neutron scattering we have studied magnetic fluctuations in 8-nm particles of antiferromagnetic {alpha}-Fe{sub 2}O{sub 3} (hematite) as a function of temperature and applied magnetic fields. The fluctuations are dominated by uniform excitations. Studies have been performed on both coated (noninteracting) and uncoated (interacting) particles. We have estimated the magnetic anisotropy energy and found that the data are in good agreement with the value obtained from Moessbauer spectroscopy. The energy {epsilon}{sub 0} of the uniform excitations depends strongly on the uncompensated moment, which is caused by finite-size effects, and we have estimated the size of this moment from the experimental neutron data. The field dependence of {epsilon}{sub 0} for the interacting nanoparticles differs strongly from that of the noninteracting nanoparticles, and this is a result of the influence of exchange interaction between the particles.

  15. ⁵⁷Fe polarization-dependent synchrotron Mössbauer spectroscopy using a diamond phase plate and an iron borate nuclear Bragg monochromator.

    PubMed

    Mitsui, Takaya; Imai, Yasuhiko; Masuda, Ryo; Seto, Makoto; Mibu, Ko

    2015-03-01

    Energy-domain (57)Fe polarization-dependent synchrotron radiation Mössbauer spectroscopy was developed by using a diamond X-ray phase plate and an iron borate nuclear Bragg monochromator. The former controls the polarization of the incident synchrotron radiation X-rays and the latter filters the (57)Fe-Mössbauer radiation with a narrow bandwidth of ∼3.4 Γ0 (Γ0 ≃ 4.7 neV: natural linewidth of the (57)Fe nucleus) from the broadband synchrotron radiation. The developed nuclear diffraction optics allowed (57)Fe-Mössbauer studies to be performed with various polarization states, i.e. linear polarization, circular polarization and non-polarization. In this paper, the spectrometer system, beam characterization, performance-test experiments and a grazing-incidence Mössbauer measurement of an isotope-enriched ((57)Fe: 95%) iron thin film are described.

  16. MSATT Workshop on Innovative Instrumentation for the In Situ Study of Atmosphere-Surface Interactions on Mars

    NASA Technical Reports Server (NTRS)

    Fegley, Bruce, Jr. (Editor); Waenke, Heinrich (Editor)

    1992-01-01

    Papers accepted for the Mars Surface and Atmosphere Through Time (MSATT) Workshop on Innovative Instruments for the In Situ Study of Atmosphere-Surface Interaction of Mars, 8-9 Oct. 1992 in Mainz, Germany are included. Topics covered include: a backscatter Moessbauer spectrometer (BaMS) for use on Mars; database of proposed payloads and instruments for SEI missions; determination of martian soil mineralogy and water content using the Thermal Analyzer for Planetary Soils (TAPS); in situ identification of the martian surface material and its interaction with the martian atmosphere using DTA/GC; mass spectrometer-pyrolysis experiment for atmospheric and soil sample analysis on the surface of Mars; and optical luminescence spectroscopy as a probe of the surface mineralogy of Mars.

  17. EPR Spectroscopic Studies of [FeFe]-Hydrogenase Maturation.

    PubMed

    Suess, Daniel L M; Britt, R David

    2015-09-01

    Proton reduction and H2 oxidation are key elementary reactions for solar fuel production. Hydrogenases interconvert H(+) and H2 with remarkable efficiency and have therefore received much attention in this context. For [FeFe]-hydrogenases, catalysis occurs at a unique cofactor called the H-cluster. In this article, we discuss ways in which EPR spectroscopy has elucidated aspects of the bioassembly of the H-cluster, with a focus on four case studies: EPR spectroscopic identification of a radical en route to the CO and CN(-) ligands of the H-cluster, tracing (57)Fe from the maturase HydG into the H-cluster, characterization of the auxiliary Fe-S cluster in HydG, and isotopic labeling of the CN(-) ligands of HydA for electronic structure studies of its Hox state. Advances in cell-free maturation protocols have enabled several of these mechanistic studies, and understanding H-cluster maturation may in turn provide insights leading to improvements in hydrogenase production for biotechnological applications.

  18. Coupling Nuclear Induced Phonon Propagation with Conversion Electron Moessbauer Spectroscopy

    DTIC Science & Technology

    2015-06-18

    global AA PEAKHEIGHTS FIXEDPARAMETERS AUTOZERO delta BIPOLAR % peakfit.m version 5, February 2014 format short g format compact warning off...NumTrials) % % Construct model from best-fit parameters AA=zeros(NumPeaks,600); =linspace(min(xx),max(xx),600); % =linspace(min(xx)-length(xx...max(xx)+length(xx),200); for m=1:NumPeaks, switch peakshape(1) case 1 AA(m,:)=gaussian( ,FitParameters(2*m-1),FitParameters(2*m

  19. Search for the Moessbauer Effect in SILVER-109

    NASA Astrophysics Data System (ADS)

    Rezaie-Serej, Shokrollah

    1992-01-01

    The 88-keV first-excited nuclear state in ^{109}Ag has a mean lifetime of 57.1 sec and a corresponding natural linewidth of 1.15 times 10^{-17 } eV which is nearly six orders of magnitude narrower than the width for the 93-keV 13.2-mu sec state in ^{67}Zn. The 93-keV transition in ^{67}Zn has the narrowest linewidth for which the Mossbauer effect has been observed. The 88-keV transition in ^ {109}Ag is obviously a very difficult case for the observation of the Mossbauer effect and provides a stringent test for exploring the practical limits of inhomogeneous line broadening in real single crystals. In the past, two attempts have produced evidence for the occurrence of the Mossbauer effect in ^{109}Ag. However, more detailed, corroborating results are needed to substantiate such positive results. This dissertation reports the results of a series of self-absorption experiments using ^{109 }Cd-doped single-crystal samples of natural silver to observe the Mossbauer effect in ^ {109}Ag. In addition to measuring the temperature dependence of the 88-keV gamma rays emanating from the samples, the changes in the accompanying x rays were also monitored to account for problems associated with the temperature dependence of the solid angle subtended by the detector. The data were analyzed by a parametric model simulating the experiments. The results of these self-absorption experiments in the vertical geometry indicated a clear, positive Mossbauer effect. The measured effective cross section was only two orders of magnitude smaller than the theoretical value of maximum resonance cross section (4.56 times 10^{-20} cm ^{2}). Such a large effective cross section implies an effective linewidth (neglecting the effect of the gravitational redshift and the ambient magnetic field) approximately 50 times the natural linewidth. This is a surprisingly small amount of broadening which is currently not understood.

  20. Very high pressure Moessbauer spectroscopy using diamond anvil cells

    SciTech Connect

    Pasternak, M.P.; Taylor, R.D.

    1988-01-01

    The technique of generating very high pressure by means of Diamond Anvil Cells (DAC) for Mossbauer Effect applications is outlined. A comprehensive description is presented of the principles of DAC, modification for the use in M/umlt o/ssbauer Spectroscopy (MS), the Merrill--Bassett and Bassett cells, of pressure measurements, of gasketing and collimation, and of hydrostatic media. Examples of /sup 151/Eu, /sup 119/Sn and /sup 129/I are given showing the feasibility of DAC applications in MS. Other isotopes with potential use for high pressure MS using DAC are suggested. 27 refs., 9 figs.

  1. Moessbauer Spectroscopy of Mineral Separates from SNC Meteorites

    NASA Technical Reports Server (NTRS)

    Dyar, M. D.

    2003-01-01

    Numerous workers have recently focused attention on the issue of the oxygen fugacity (f(sub O2)) of martian samples. Estimates of fO2 based on Fe-Ti oxides and D(sub Eu)/D(sub Gd) and D(sub Eu)/D(sub Sm) ratios suggest a range of fO2 values for SNC meteorites from IW+2.5 - IW+3.5 for Shergotty to IW- 2.0 - IW+0.2 for QUE94201. Fe(3+)/Fe(2+) is also a function of f(sub O2), and synchrotron micro-XANES values for olivine, pyroxene, and feldspar Fe(3+) have been reported. However, the relationship between the reported Fe(3+) values and the other methods for estimating f(sub O2) is not clear, and further measurements of Fe(3+)/Fe(2+) by a more conventional technique have been needed. Accordingly, in this project, new Mossbauer spectroscopy data on mineral separates handpicked from 10 SNC meteorites are reported.

  2. Moessbauer spectra of ferrite catalysts used in oxidative dehydrogenation

    NASA Technical Reports Server (NTRS)

    Cares, W. R.; Hightower, J. W.

    1971-01-01

    Room temperature Mossbauer spectroscopy was used to examine bulk changes which occur in low surface area CoFe2O4 and CuFe2O4 catalysts as a result of contact with various mixtures of trans-2-butene and O2 during oxidative dehydrogenation reactions at about 420 C. So long as there was at least some O2 in the gas phase, the CoFe2O4 spectrum was essentially unchanged. However, the spectrum changed from a random spinel in the oxidized state to an inverse spinel as it was reduced by oxide ion removal. The steady state catalyst lies very near the fully oxidized state. More dramatic solid state changes occurred as the CuFe2O4 underwent reduction. Under severe reduction, the ferrite was transformed into Cu and Fe3O4, but it could be reversibly recovered by oxidation. An intense doublet located near zero velocity persisted in all spectra of CuFe2O4 regardless of the state of reduction.

  3. Insights into iron sources and pathways in the Amazon River provided by isotopic and spectroscopic studies

    NASA Astrophysics Data System (ADS)

    Mulholland, Daniel Santos; Poitrasson, Franck; Boaventura, Geraldo Resende; Allard, Thierry; Vieira, Lucieth Cruz; Santos, Roberto Ventura; Mancini, Luiz; Seyler, Patrick

    2015-02-01

    The present study investigated the weathering and transport mechanisms of Fe in the Amazon River. A particular emphasis was placed on Fe partitioning, speciation, and isotopic fractionation in the contrasting waters of the Solimões and Negro rivers and their mixing zone at the beginning of the Amazon River. Samples collected in the end-member rivers and thirteen sites distributed throughout the mixing zone were processed through frontal vacuum filtration and tangential-flow ultrafiltration to separate the different suspended solid fractions, i.e., particulate (P > 0.45 μm and P > 0.22 μm), colloidal (0.22 μm > C > 5 kDa) and truly dissolved elements (TD < 5 kDa). The Fe isotopic composition and electron paramagnetic resonance (EPR) species were measured on these different pore-sized fractions. The acidic and organo-Fe-rich waters of the Negro River displayed dissolved and colloidal fractions enriched in heavy isotopes (∼1.2‰, in δ57Fe values relative to IRMM-14), while the particulate fractions yielded light isotopic compositions of -0.344‰ for P > 0.22 μm and -0.104‰ for P > 0.45 μm fractions). The mineral particulate-rich waters of the Solimões River had dissolved and colloidal fractions with light isotopic composition (-0.532‰ and -0.176‰, respectively), whereas the particulate fractions yielded δ57Fe values close to those of the continental crust (i.e., -0.029‰ for P > 0.22 μm and 0.028‰ for P > 0.45 μm). Ten kilometers downstream from the Negro and Solimões junction, the concentrations of colloidal and dissolved Fe species deviate markedly from conservative mixing. A maximum Fe loss of 43 μg/L (i.e., 50% of the dissolved and colloidal Fe) is observed 110 km downstream from the rivers junction. The contrasting Negro and Solimões Rivers isotopic compositions along the pore-sized water fractions is attributable to the biogeochemical processes involving different types of upland soils and parental materials. For instance, the isotopic

  4. Thermal Decomposition of Almandine Garnet: Mössbauer Study

    NASA Astrophysics Data System (ADS)

    Barcova, K.; Mashlan, M.; Zboril, R.; Martinec, P.; Kula, P.

    2001-07-01

    The thermal decomposition of almandine garnet from Zoltye Vody, Ukraine, has been studied using57Fe Mössbauer spectroscopy. Room temperature Mössbauer spectrum of the initial powdered sample is characterised by one doublet corresponding to Fe2+ in dodecahedral position 24c. In the room temperature spectra of all heated almandine samples, a doublet corresponding to γ-Fe2O3 nanoparticles appeared. Depending on experimental conditions (heating temperature and time), the additional spectral lines of α-Fe2O3 and ɛ-Fe2O3 were observed in Mössbauer spectra. It is obvious that the thermal transformation of almandine garnet in air is related to the primary formation of γ-Fe2O3 superparamagnetic nanoparticles. γ-Fe2O3 nanoparticles are transformed into ɛ-Fe2O3 and consequently into α-Fe2O3 at higher temperatures. The mechanism and kinetics of the individual structural transformations depend on experimental conditions — mainly on the heating temperature and size of the particles.

  5. Mössbauer and XRD study of Al-Sn linished steel bimetal alloy

    NASA Astrophysics Data System (ADS)

    Kuzmann, E.; Silva, L. da; Stichleutner, S.; El-Sharif, M.; Homonnay, Z.; Klencsár, Z.; Sziráki, L.; Chisholm, C. U.; Lak, B.

    2016-12-01

    Aluminium alloy free CS1 type steel (0.06 wt% C, 0.45 wt% Mn) and samples of cold roll bonded steel bimetal alloys (MAS15 and MAS16) were fabricated and investigated by X-ray diffraction (XRD), 57Fe conversion electron Mössbauer spectroscopy (CEMS) at room temperature. XRD has revealed only the existence of the alpha iron solid solution (steel) phase in the steel only sample, while identified steel and metallic Al and Sn constituent phases in the bimetallic alloys. 57Fe Mössbauer spectroscopy revealed the presence of 4 % secondary iron-bearing phase attributed mainly to iron oxide/ oxyhydroxides (ferrihydrite) besides the steel matrix on the surface of the steel sample. A significant difference between the occurrences of the secondary phase of differently prepared bimetal alloys found in their 57Fe CEM spectra allowed to identify the main phase of debris as different iron oxide/ oxyhydroxides.

  6. Structural, thermal, magnetic and electrical studies of the iron oxophosphate Rb{sub 7}Fe{sub 7}(PO{sub 4}){sub 8}O{sub 2}.2H{sub 2}O

    SciTech Connect

    Hidouri, Mourad; Lajmi, Besma; Gmati, Nadia; Wattiaux, Alain; Nenert, Gwilherm; Ritter, Clemens; Fournes, Leopold; Darriet, Jacques; Lopez, Maria Luisa; Pico, Carlos; Amara, Mongi B.

    2010-09-15

    A new iron oxophosphate of composition Rb{sub 7}Fe{sub 7}(PO{sub 4}){sub 8}O{sub 2}.2H{sub 2}O has been synthesized and studied by X-ray diffraction, TG and DTA analysis, magnetic susceptibility, neutron diffraction, Moessbauer spectroscopy and ionic conductivity. This compound crystallizes in the monoclinic system with the P2{sub 1}/c space group and the unit cell parameters a = 8.224(8) A, b = 22.162(6) A, c = 9.962(6) A and {beta} = 109.41(8){sup o}. Its structure is built up from Fe{sub 7}O{sub 32} clusters of edge- and corner-sharing FeO{sub 5} and FeO{sub 6} polyhedra. Neighboring clusters are connected by the phosphate tetrahedra to form a three-dimensional framework. The Rb{sup +} cations and the water molecules are occupying intersecting tunnels parallel to a and c. The presence of water molecules was confirmed by TG and DTA analysis. The magnetic susceptibility measurements have shown the existence of antiferromagnetic ordering below 22 K with a weak ferromagnetic component. Additionally, these measurements show evidence for a strong magnetic frustration characterized by |{theta}/T{sub N}| {approx} 12. Powder neutron diffraction study confirms the presence of a long range antiferromagnetic order coupled to a weak ferromagnetic component along the b-axis. The strongly reduced magnetic moments extracted from the refinement support the existence of a magnetically frustrated ground state. The Moessbauer spectroscopy results confirmed the presence of only Fe{sup 3+} ions in both five and six coordination. The ionic conductivity measurements led to activation energy of 0.81 eV, a value that agrees with the obtained for other rubidium phosphates.

  7. Iron-rich Oxides at the Core-mantle Boundary

    NASA Astrophysics Data System (ADS)

    Wicks, J. K.; Jackson, J. M.; Sturhahn, W.; Bower, D. J.; Zhuravlev, K. K.; Prakapenka, V.

    2013-12-01

    Seismic observations near the base of the core-mantle boundary (CMB) have detected 5-20 km thick patches in which the seismic wave velocities are reduced by up to 30%. These ultra-low velocity zones (ULVZs) have been interpreted as aggregates of partially molten material (e.g. Williams and Garnero 1996, Hernlund and Jellinek, 2010) or as solid, iron-enriched residues (e.g. Knittle and Jeanloz, 1991; Mao et al., 2006; Wicks et al., 2010), typically based on proposed sources of velocity reduction. The stabilities of these structure types have been explored through dynamic models that have assembled a relationship between ULVZ stability and density (Hernlund and Tackley, 2007; Bower et al., 2010). Now, to constrain the chemistry and mineralogy of ULVZs, more information is needed on the relationship between density and sound velocity of candidate phases. We present the pressure-volume-temperature equation of state of (Mg0.06 57Fe0.94)O determined up to pressures of 120 GPa and temperatures of 2000 K. Volume was measured with X-ray diffraction at beamline 13-ID-D of the Advanced Photon Source (APS), where high pressures and temperatures are achieved in a diamond anvil cell with in-situ laser heating. Sample assemblies were prepared using dehydrated NaCl as an insulator and neon as a pressure transmitting medium. We present results with and without iron as a buffer and thermal pressure gauge. We have also determined the room temperature Debye velocity (VD) of (Mg0.06 57Fe0.94)O using nuclear resonant inelastic x-ray scattering and in-situ X-ray diffraction, up to 80 GPa at 3-ID-B of the APS. The effect of the electronic environment of the iron sites on the velocities was tracked in-situ using synchrotron Moessbauer spectroscopy. Using our measured equation of state, the seismically relevant compressional (VP) and shear (VS) wave velocities were calculated from the Debye velocities. We combine these studies with a simple mixing model to predict the properties of a solid

  8. An FTIR and ESR study of iron doped calcium borophosphate glass-ceramics

    NASA Astrophysics Data System (ADS)

    Karabulut, M.; Popa, A.; Borodi, G.; Stefan, R.

    2015-12-01

    A series of glasses in the xFe2O3-(100-x) [42B2O3-24CaO-34P2O5] system has been prepared for x = 0-10. Structure of as casted glasses and their heat treated counterparts have been studied by X-ray diffraction, infrared and electron spin resonance spectroscopies. Amorphous nature of all of the compositions studied is confirmed by the XRPD spectra. After the heat treatment, besides the main BPO4 phase, CaBPO5 and Ca(PO3) crystalline phases were identified in the iron free glass while B0.57Fe0.43PO4 phase was also observed in the XRD pattern of iron containing samples. FTIR spectra indicate changes in the glass network upon iron addition. X-band ESR spectra exhibits resonance signals at g ∼ 2.0 and g ∼ 4.3 for all analyzed samples. A supplementary line centered at g ∼ 6 appears after the thermal treatment. The nature of ESR absorption signals and influence of iron content on the evolution of ESR parameters are discussed.

  9. Recent advances in biosynthetic modeling of nitric oxide reductases and insights gained from nuclear resonance vibrational and other spectroscopic studies.

    PubMed

    Chakraborty, Saumen; Reed, Julian; Sage, J Timothy; Branagan, Nicole C; Petrik, Igor D; Miner, Kyle D; Hu, Michael Y; Zhao, Jiyong; Alp, E Ercan; Lu, Yi

    2015-10-05

    This Forum Article focuses on recent advances in structural and spectroscopic studies of biosynthetic models of nitric oxide reductases (NORs). NORs are complex metalloenzymes found in the denitrification pathway of Earth's nitrogen cycle where they catalyze the proton-dependent two-electron reduction of nitric oxide (NO) to nitrous oxide (N2O). While much progress has been made in biochemical and biophysical studies of native NORs and their variants, a clear mechanistic understanding of this important metalloenzyme related to its function is still elusive. We report herein UV-vis and nuclear resonance vibrational spectroscopy (NRVS) studies of mononitrosylated intermediates of the NOR reaction of a biosynthetic model. The ability to selectively substitute metals at either heme or nonheme metal sites allows the introduction of independent (57)Fe probe atoms at either site, as well as allowing the preparation of analogues of stable reaction intermediates by replacing either metal with a redox inactive metal. Together with previous structural and spectroscopic results, we summarize insights gained from studying these biosynthetic models toward understanding structural features responsible for the NOR activity and its mechanism. The outlook on NOR modeling is also discussed, with an emphasis on the design of models capable of catalytic turnovers designed based on close mimics of the secondary coordination sphere of native NORs.

  10. Model compounds of iron gall inks - a Mössbauer study

    NASA Astrophysics Data System (ADS)

    Lerf, A.; Wagner, F. E.

    2016-12-01

    Ferrogallic inks were used for at least two millennia before they became obsolete in the 20th century. The chemistry of such inks is, however, still largely unclear. Today it is of particular interest for the conservation of old manuscripts. 57Fe Mössbauer spectra of the ink on historical documents showed the presence of Fe(II) oxalate and of Fe(III) sites presumably representing iron oxihydroxides. To obtain more information on the behaviour of ink on paper we have performed Mössbauer studies at 300 and 4.2 K on iron gall inks prepared from FeSO4ṡ7H2O and tannin. These inks were either written on paper or isolated as a precipitate by centrifugation. In the dried precipitate there is still a strong contribution of the FeSO4ṡ7H2O which is absent in the same ink written on paper, for which a broad ferrous component with a quadrupole splitting (QS) of about 2.5 mm/s was found. The dominant Fe(III) site present in all inks on paper with QS ≈ 0.82 mm/s is not Fe(III) gallate and different from the precipitates. We propose that nanoparticulate oxidic clusters or molecular composites covered by a shell of polymerized oxidation products of the phenols are formed on the paper.

  11. Early Pottery Making in Northern Coastal Peru. Part I: Mössbauer Study of Clays

    NASA Astrophysics Data System (ADS)

    Shimada, I.; Häusler, W.; Hutzelmann, T.; Wagner, U.

    2003-09-01

    We report on an investigation of several ancient clays which were used for pottery making in northern coastal Peru at a kiln site from the Formative period (ca. 2000-800 BC) in the Poma Canal and at a Middle Sicán pottery workshop in use between ca. AD 950 and 1050 at Huaca Sialupe in the lower La Leche valley. Neutron activation analysis, 57Fe Mössbauer spectroscopy and X-ray diffraction were used for the characterisation of the clays. The changes that occur in iron-bearing compounds in the clays depending on the kiln atmosphere and on the maximum firing temperature were studied by Mössbauer spectroscopy and X-ray diffraction. Laboratory firing series under varying controlled conditions were performed to obtain a basic understanding of the different reactions taking place in the clays during firing. The results can be used as models in the interpretation of the Mössbauer spectra observed in ancient ceramics from the same context.

  12. Mössbauer Study of Graphite-Containing Iron Oxide Nanoparticles

    NASA Astrophysics Data System (ADS)

    Sorescu, Monica; Trotta, Richard

    2016-03-01

    Graphite-doped hematite and magnetite nanoparticles systems (~50 nm) were prepared by mechanochemical activation for milling times ranging from 2 to 12 hours. Their structural and magnetic properties were studied by 57Fe Mössbauer spectroscopy. The spectra corresponding to the hematite milled samples were analyzed by considering two sextets, corresponding to the incorporation of carbon atoms into the iron oxide structure. For ball-milling time of 12 hours a quadrupole split doublet has been added, representing the contribution of ultrafine particles. The Mössbauer spectra of graphite-doped magnetite were resolved considering a sextet and a magnetic hyperfine field distribution, corresponding to the tetrahedral and octahedral sublattices of magnetite, respectively. A quadrupole split doublet was incorporated in the fitting of the 12-hour milled sample. The recoilless fraction for all samples was determined using our previously developed dual absorber method. It was found that the recoilless fraction of the graphite-doped hematite nanoparticles decreases as function of ball-milling time. The f factor of graphite-containing magnetite nanoparticles for the tetrahedral sites stays constant, while that of the octahedral sublattice decreases as function of ball-milling time. These findings reinforce the idea that carbon atoms exhibit preference for the octahedral sites of magnetite.

  13. New iron tetrazolate frameworks: synthesis, temperature effect, thermal behaviour, Mössbauer and magnetic studies.

    PubMed

    Pimenta, Vanessa; Le, Quang Hoang Hanh; Clark, Lucy; Lhoste, Jérôme; Hémon-Ribaud, Annie; Leblanc, Marc; Grenèche, Jean-Marc; Dujardin, Gilles; Lightfoot, Philip; Maisonneuve, Vincent

    2015-05-07

    The exploration of the FeF3/FeF2-Hamtetraz-HF system in dimethylformamide by solvothermal synthesis evidences two isostructural 3D hybrid fluoroferrates. They are prepared from the same starting mixture at two different synthesis temperatures: 120 °C for [Hdma]·(Fe4(II)Fe(III)F8(H2O)2(amtetraz)4) () and 140 °C for [Hdma]1.5·(Fe4.5(II)Fe0.5(III)F7(H2O)(HCOO)(amtetraz)4) (). Both compounds are characterized by single crystal X-ray diffraction, X-ray thermodiffraction, TGA analysis, Mössbauer spectrometry and SQUID magnetometry. They crystallize in the monoclinic system and are built from two distinct chains connected by aminotetrazolate anions. The first chain ∞(Fe(II)FN4) is common to and and can be found in numerous fluorides. In the second chain ∞(Fe3X12) (X = F, N, O), iron cations adopt both valence states Fe(ii)/Fe(iii). The hydrolysis of DMF implies the formation of a [Hdma](+) cation and a (HCOO)(-) anion. The presence of Fe(3+) in both phases is evidenced by (57)Fe Mössbauer spectrometry. The magnetic properties are studied and two transitions from a paramagnetic regime to a long range ordered state below 30 K and 5 K are identified.

  14. Iron absorption in raw and cooked bananas: a field study using stable isotopes in women

    PubMed Central

    García, Olga P.; Martínez, Mara; Romano, Diana; Camacho, Mariela; de Moura, Fabiana F.; Abrams, Steve A.; Khanna, Harjeet K.; Dale, James L.; Rosado, Jorge L.

    2015-01-01

    Background Banana is a staple food in many regions with high iron deficiency and may be a potential vehicle for iron fortification. However, iron absorption from bananas is not known. Objective The objective of this study was to evaluate total iron absorption from raw and cooked bananas. Design Thirty women (34.9±6.6 years) from rural Mexico were randomly assigned to one of two groups each consuming: 1) 480 g/day of raw banana for 6 days, or 2) 500 g/day of cooked banana for 4 days. Iron absorption was measured after extrinsically labeling with 2 mg of 58Fe and a reference dose of 6 mg 57Fe; analysis was done using ICP-MS. Results Iron content in cooked bananas was significantly higher than raw bananas (0.53 mg/100 g bananas vs. 0.33 mg/100 mg bananas, respectively) (p<0.001). Percent iron absorption was significantly higher in raw bananas (49.3±21.3%) compared with cooked banana (33.9±16.2%) (p=0.035). Total amount of iron absorbed from raw and cooked bananas was similar (0.77±0.33 mg vs. 0.86±0.41 mg, respectively). Conclusion Total amount of absorbed iron is similar between cooked and raw bananas. The banana matrix does not affect iron absorption and is therefore a potential effective target for genetic modification for iron biofortification. PMID:25660254

  15. Iron absorption in raw and cooked bananas: a field study using stable isotopes in women.

    PubMed

    García, Olga P; Martínez, Mara; Romano, Diana; Camacho, Mariela; de Moura, Fabiana F; Abrams, Steve A; Khanna, Harjeet K; Dale, James L; Rosado, Jorge L

    2015-01-01

    Banana is a staple food in many regions with high iron deficiency and may be a potential vehicle for iron fortification. However, iron absorption from bananas is not known. The objective of this study was to evaluate total iron absorption from raw and cooked bananas. Thirty women (34.9±6.6 years) from rural Mexico were randomly assigned to one of two groups each consuming: 1) 480 g/day of raw banana for 6 days, or 2) 500 g/day of cooked banana for 4 days. Iron absorption was measured after extrinsically labeling with 2 mg of (58)Fe and a reference dose of 6 mg (57)Fe; analysis was done using ICP-MS. Iron content in cooked bananas was significantly higher than raw bananas (0.53 mg/100 g bananas vs. 0.33 mg/100 mg bananas, respectively) (p<0.001). Percent iron absorption was significantly higher in raw bananas (49.3±21.3%) compared with cooked banana (33.9±16.2%) (p=0.035). Total amount of iron absorbed from raw and cooked bananas was similar (0.77±0.33 mg vs. 0.86±0.41 mg, respectively). Total amount of absorbed iron is similar between cooked and raw bananas. The banana matrix does not affect iron absorption and is therefore a potential effective target for genetic modification for iron biofortification.

  16. Fe isotope fractionation between chalcopyrite and dissolved Fe during hydrothermal recrystallization: An experimental study at 350 °C and 500 bars

    NASA Astrophysics Data System (ADS)

    Syverson, Drew D.; Luhmann, Andrew J.; Tan, Chunyang; Borrok, David M.; Ding, Kang; Seyfried, William E.

    2017-03-01

    Equilibrium Fe isotope fractionation between chalcopyrite and dissolved Fe was determined in acidic chloride-bearing fluid at 350 °C and 500 bars. The study utilized deformable gold-cell technology, which allowed time-series sampling of solution during chalcopyrite recrystallization and isotope exchange. A key element of the experimental design involved the addition of anomalous dissolved 57Fe to an on-going experiment as a means of determining the degree and rate of isotope exchange. Taking explicit account of imposed chemical and isotopic mass balance constraints of Fe in fluid and mineral (chalcopyrite) reservoirs, these data indicate that no more than 1000 h is required for the isotopically anomalous dissolved Fe reservoir to exchange completely with the coexisting chalcopyrite. The experimental calibration of the rate of Fe isotope exchange for the δ57Fe-spiked experiment provides critical insight for the time necessary to achieve Fe isotope exchange in two non-spiked, but otherwise identical experiments. The Fe isotope data indicate that the equilibrium fractionation between chalcopyrite and dissolved Fe, Δ56FeCpy-Fe (aq), at 350 °C is small, 0.09 ± 0.17‰ (2σ), and is in good agreement with recent theoretical equilibrium predictions. Owing to the apparent rate of Fe isotope exchange at 350 °C, it is likely that chalcopyrite formed at high temperature deep-sea vents (black smoker systems) achieves isotopic equilibrium, and effectively records the Fe isotopic composition of the coexisting end-member hydrothermal fluid. Comparison of the experimental mineral-fluid equilibrium fractionation factors with conjugate chalcopyrite and dissolved Fe pairs sampled from high temperature hydrothermal vent systems at Axial Caldera and Main Endeavour Field (Juan de Fuca Ridge) are in agreement with this inference. The experimental data were further used to determine the mineral-mineral equilibrium Fe isotope fractionation between pyrite-chalcopyrite, Δ56Fe

  17. H-bonding scheme and cation partitioning in axinite: a single-crystal neutron diffraction and Mössbauer spectroscopic study

    NASA Astrophysics Data System (ADS)

    Gatta, G. Diego; Redhammer, Günther J.; Guastoni, Alessandro; Guastella, Giorgio; Meven, Martin; Pavese, Alessandro

    2016-05-01

    The crystal chemistry of a ferroaxinite from Colebrook Hill, Rosebery district, Tasmania, Australia, was investigated by electron microprobe analysis in wavelength-dispersive mode, inductively coupled plasma-atomic emission spectroscopy (ICP-AES), 57Fe Mössbauer spectroscopy and single-crystal neutron diffraction at 293 K. The chemical formula obtained on the basis of the ICP-AES data is the following: ^{X1,X2} {{Ca}}_{4.03} Y ( {{{Mn}}_{0.42} {{Mg}}_{0.23} {{Fe}}^{2 + }_{1.39} } )_{Σ 2.04} ^{Z1,Z2} ( {{{Fe}}^{3 + }_{0.15} {{Al}}_{3.55} {{Ti}}_{0.12} } )_{Σ 3.82} ^{T1,T2,T3,T4} ( {{{Ti}}_{0.03} {{Si}}_{7.97} } )_{Σ 8} ^{T5} {{B}}_{1.96} {{O}}_{30} ( {{OH}} )_{2.18} . The 57Fe Mössbauer spectrum shows unambiguously the occurrence of Fe2+ and Fe3+ in octahedral coordination only, with Fe2+/Fe3+ = 9:1. The neutron structure refinement provides a structure model in general agreement with the previous experimental findings: the tetrahedral T1, T2, T3 and T4 sites are fully occupied by Si, whereas the T5 site is fully occupied by B, with no evidence of Si at the T5, or Al or Fe3+ at the T1- T5 sites. The structural and chemical data of this study suggest that the amount of B in ferroaxinite is that expected from the ideal stoichiometry: 2 a.p.f.u. (for 32 O). The atomic distribution among the X1, X2, Y, Z1 and Z2 sites obtained by neutron structure refinement is in good agreement with that based on the ICP-AES data. For the first time, an unambiguous localization of the H site is obtained, which forms a hydroxyl group with the oxygen atom at the O16 site as donor. The H-bonding scheme in axinite structure is now fully described: the O16- H distance (corrected for riding motion effect) is 0.991(1) Å and an asymmetric bifurcated bonding configuration occurs, with O5 and O13 as acceptors [i.e. with O16··· O5 = 3.096(1) Å, H··· O5 = 2.450(1) Å and O16- H··· O5 = 123.9(1)°; O16··· O13 = 2.777(1) Å, H··· O13 = 1.914(1) Å and O16- H··· O13 = 146

  18. Iron(II)-Catalyzed Iron Atom Exchange and Mineralogical Changes in Iron-rich Organic Freshwater Flocs: An Iron Isotope Tracer Study.

    PubMed

    ThomasArrigo, Laurel K; Mikutta, Christian; Byrne, James; Kappler, Andreas; Kretzschmar, Ruben

    2017-06-20

    In freshwater wetlands, organic flocs are often found enriched in trace metal(loid)s associated with poorly crystalline Fe(III)-(oxyhydr)oxides. Under reducing conditions, flocs may become exposed to aqueous Fe(II), triggering Fe(II)-catalyzed mineral transformations and trace metal(loid) release. In this study, pure ferrihydrite, a synthetic ferrihydrite-polygalacturonic acid coprecipitate (16.7 wt % C), and As- (1280 and 1230 mg/kg) and organic matter (OM)-rich (18.1 and 21.8 wt % C) freshwater flocs dominated by ferrihydrite and nanocrystalline lepidocrocite were reacted with an isotopically enriched (57)Fe(II) solution (0.1 or 1.0 mM Fe(II)) at pH 5.5 and 7. Using a combination of wet chemistry, Fe isotope analysis, X-ray absorption spectroscopy (XAS), (57)Fe Mössbauer spectroscopy and X-ray diffraction, we followed the Fe atom exchange kinetics and secondary mineral formation over 1 week. When reacted with Fe(II) at pH 7, pure ferrihydrite exhibited rapid Fe atom exchange at both Fe(II) concentrations, reaching 76 and 89% atom exchange in experiments with 0.1 and 1 mM Fe(II), respectively. XAS data revealed that it transformed into goethite (21%) at the lower Fe(II) concentration and into lepidocrocite (73%) and goethite (27%) at the higher Fe(II) concentration. Despite smaller Fe mineral particles in the coprecipitate and flocs as compared to pure ferrihydrite (inferred from Mössbauer-derived blocking temperatures), these samples showed reduced Fe atom exchange (9-30% at pH 7) and inhibited secondary mineral formation. No release of As was recorded for Fe(II)-reacted flocs. Our findings indicate that carbohydrate-rich OM in flocs stabilizes poorly crystalline Fe minerals against Fe(II)-catalyzed transformation by surface-site blockage and/or organic Fe(II) complexation. This hinders the extent of Fe atom exchange at mineral surfaces and secondary mineral formation, which may consequently impair Fe(II)-activated trace metal(loid) release. Thus, under short

  19. Unusual 5f magnetism in the U2Fe3Ge ternary Laves phase: a single crystal study.

    PubMed

    Henriques, M S; Gorbunov, D I; Waerenborgh, J C; Havela, L; Shick, A B; Diviš, M; Andreev, A V; Gonçalves, A P

    2013-02-13

    Magnetic properties of the intermetallic compound U(2)Fe(3)Ge were studied on a single crystal. The compound crystallizes in the hexagonal Mg(2)Cu(3)Si structure, an ordered variant of the MgZn(2) Laves structure (C14). U(2)Fe(3)Ge displays ferromagnetic order below the Curie temperature T(C) = 55 K and presents an exception to the Hill rule, as the nearest inter-uranium distances do not exceed 3.2 Å. Magnetic moments lie in the basal plane of the hexagonal lattice, with the spontaneous magnetic moment M(s) = 1.0 μ(B)/f.u. at T = 2 K. No anisotropy within the basal plane is detected. In contrast to typical U-based intermetallics, U(2)Fe(3)Ge exhibits very low magnetic anisotropy, whose field does not exceed 10 T. The dominance of U in the magnetism of U(2)Fe(3)Ge is suggested by the (57)Fe Mössbauer spectroscopy study, which indicates very low or even zero Fe moments. Electronic structure calculations are in agreement with the observed easy-plane anisotropy but fail to explain the lack of an Fe contribution to the magnetism of U(2)Fe(3)Ge.

  20. Mössbauer and calorimetric studies of portland cement hydration in the presence of black gram pulse

    NASA Astrophysics Data System (ADS)

    Rai, Sarita; Kurian, Sajith; Dwivedi, V. N.; Das, S. S.; Singh, N. B.; Gajbhiye, N. S.

    2009-01-01

    Effect of different concentrations of naturally occurring admixture in the form of fine powder of black gram pulse (BGP) on the hydration of Portland cement was studied by isothermal calorimetry and 57Fe Mössbauer spectroscopy. The spectra were recorded for anhydrous cement and the hydration products at room temperature and 77 K. In the presence of BGP, the spectra showed superparamagnetic doublets at room temperature and the sextet at 77 K, due to the presence of fine particles of iron containing component. Mössbauer studies of hydration products confirmed the formation of nanosize hydration products containing Fe3 + . The isomer shift ( δ) and the quadrupole splitting (Δ E Q) values of C4AF in the cement confirmed iron in an octahedral and tetrahedral environment with +3 oxidation state. The high value of quadrupole splitting showed the high asymmetry of the electron environment around the iron atom. The overall mechanism of the hydration of cement in presence of BGP is discussed.

  1. Cobalt(II) complexation with small biomolecules as studied by 57Co emission Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Kamnev, Alexander A.; Perfiliev, Yurii D.; Kulikov, Leonid A.; Tugarova, Anna V.; Kovács, Krisztina; Homonnay, Zoltán; Kuzmann, Ernő

    2017-02-01

    In the emission (57Co) variant of Mössbauer spectroscopy (EMS), the 57Co radionuclide (with a half-life of 9 months) is used that undergoes a nuclear decay 57Co → 57Fe via electron capture followed by the emission of a γ-quantum, the energy of which is modified by the chemical state and the close coordination environment of the parent 57Co atom. While EMS has been used largely in materials science and nuclear chemistry, its high sensitivity can also be of great advantage in revealing fine structural features and for speciation analysis of biological complexes, whenever the 57Co2 + cation can be used directly as the coordinating metal or as a substitute for native cobalt or other metal ions. As such EMS applications are yet rare, in order to reliably interpret emission spectra of sophisticated 57Co2 +-doped biosystems, model EMS studies of simple cobalt biocomplexes are necessary. In this work, EMS spectroscopic data are analysed and discussed for 57Co2 + complexes with a range of small biomolecules of different structures, including 4-n-hexylresorcinol, homoserine lactone and a few amino acids (spectra measured in rapidly frozen dilute aqueous solutions or in the dried state at T = 80 K). The EMS data obtained are discussed with regard to the available literature data related to the coordination modes of the biocomplexes under study.

  2. Stabilization of Ca1-dFe2-xMnxO4 (0.44 lt x lt 2) with CaFe2O4-type Structure and Ca2plus Defects in 1D Channels

    SciTech Connect

    T Yang; M Croft; A Ignatov; I Nowik; R Cong; M Greenblatt

    2011-12-31

    Solid solutions of Ca{sub 1-{delta}}Fe{sub 2-x}Mn{sub x}O{sub 4} (0.45 {<=} x {<=} 2) were synthesized from CaCl{sub 2} as flux at 850 C in air. The entire series, even with x = 2, crystallizes in the CaFe{sub 2}O{sub 4}-type structure (Pnma), rather than in the CaMn{sub 2}O{sub 4}-type structure (Pbcm). Rietveld refinements confirmed mixed-valency Mn{sup 3+}/Mn{sup 4+} and a substantial level of Ca{sup 2+} deficiency ({delta} {approx} 0.25) at high x. With increasing x, the unit-cell dimensions a and b decrease, while that of c increases. Detailed structural analyses, together with Mn K-edge X-ray absorption and {sup 57}Fe Moessbauer spectroscopy studies, revealed that the stabilization of CaFe{sub 2}O{sub 4}-type structure, even at high values of x, is due to the existence of non-Jahn-Teller active Mn{sup 4+} (and Fe{sup 3+}), which is compensated by the formation of the Ca{sup 2+} deficiencies in the one-dimensional (1D) channels of Ca{sub 1-{delta}}Fe{sub 2-x}Mn{sub x}O{sub 4} during the flux synthesis. Antiferromagnetic (AFM) long-range ordering is achieved for all compounds at low temperature, because of strong AFM interactions between Mn{sup 3+}/Mn{sup 4+} and Fe{sup 3+}. In addition, a spin (or cluster) glass component was also observed, as expected, because of the extensive Mn/Fe structural and Mn{sup 3+}/Mn{sup 4+} charge disordering.

  3. (TAML)Fe**IV=O Complex in Aqueous Solution: Synthesis And Spectroscopic And Computational Characterization

    SciTech Connect

    Chanda, A.; Shan, X.; Chakrabarti, M.; Ellis, W.C.; Popescu, D.L.; Oliveira, F.Tiago de; Wang, D.; Que, L.; Jr.; Collins, T.J.; Munck, E.; Bominaar, E.L.

    2009-05-12

    Recently, we reported the characterization of the S = 1/2 complex [Fe{sup V}(O)B*]{sup -}, where B* belongs to a family of tetraamido macrocyclic ligands (TAMLs) whose iron complexes activate peroxides for environmentally useful applications. The corresponding one-electron reduced species, [Fe{sup IV}(O)B*]{sup 2-} (2), has now been prepared in >95% yield in aqueous solution at pH > 12 by oxidation of [Fe{sup III}(H{sub 2}O)B*]{sup -} (1), with tert-butyl hydroperoxide. At room temperature, the monomeric species 2 is in a reversible, pH-dependent equilibrium with dimeric species [B*Fe{sup IV}?O?Fe{sup IV}B*]{sup 2-} (3), with a pK{sub a} near 10. In zero field, the Moessbauer spectrum of 2 exhibits a quadrupole doublet with {Delta}E{sub Q} = 3.95(3) mm/s and {delta} = ?0.19(2) mm/s, parameters consistent with a S = 1 Fe{sup IV} state. Studies in applied magnetic fields yielded the zero-field splitting parameter D = 24(3) cm{sup -1} together with the magnetic hyperfine tensor A/g{sub n}{beta}{sub n} = (?27, ?27, +2) T. Fe K-edge EXAFS analysis of 2 shows a scatterer at 1.69 (2) {angstrom}, a distance consistent with a Fe{sup IV} = O bond. DFT calculations for [Fe{sup IV}(O)B*]{sup 2-} reproduce the experimental data quite well. Further significant improvement was achieved by introducing hydrogen bonding of the axial oxygen with two solvent-water molecules. It is shown, using DFT, that the {sup 57}Fe hyperfine parameters of complex 2 give evidence for strong electron donation from B* to iron.

  4. Mössbauer studies of the peculiar magnetism in parent compounds of the iron-based superconductors

    NASA Astrophysics Data System (ADS)

    Jasek, A. K.; Komędera, K.; Błachowski, A.; Ruebenbauer, K.; Żukrowski, J.; Bukowski, Z.; Karpinski, J.

    2015-02-01

    A review of the magnetism in the parent compounds of the iron-based superconductors is given based on the transmission Mössbauer spectroscopy of 57Fe and 151Eu. It was found that the 3d magnetism is of the itinerant character with varying admixture of the spin-polarized covalent bonds. For the '122' compounds, a longitudinal spin density wave (SDW) develops. In the case of the EuFe2As2, a divalent europium arranges in an anti-ferromagnetical order at a much lower temperature as compared with the onset of SDW. These two magnetic systems remain almost uncoupled one to another. For the non-stoichiometric Fe1+xTe parent of the '11' family, one has a transversal SDW and magnetic order of the interstitial iron with relatively high and localized magnetic moments. These two systems are strongly coupled one to another. For the 'grand parent' of the iron-based superconductors FeAs, one observes two mutually orthogonal phase-related transversal SDW on the iron sites. There are two sets of such spin arrangements due to two crystallographic iron sites. The FeAs exhibits the highest covalency among the compounds studied, but it has still a metallic character. A contribution to XVI National Conference on Superconductivity, Zakopane, Poland, 7-12 October 2013.

  5. Studies of iron impurities in YxPr1-xBa2Cu3O7-delta

    NASA Technical Reports Server (NTRS)

    Swartzendruber, L. J.; Bennett, L. H.; Ritter, J.; Rubinstein, M.; Harford, M. Z.

    1990-01-01

    Pr is the only rare earth which, when substituted for Y in YBa2Cu3O7, significantly alters the superconducting transition temperature T(sub c) without changing the crystal structure. For YxPr1-xBa2Cu3O7-delta with delta approx. equal to 0, T(sub c) is reduced rapidly as x is increased, reaching zero for x about 0.5. For x above 0.5 the compound is antiferromagnetic with a Neel temperature that increases with increasing x, rising to above room temperature for x near 1. A similar behavior is observed when the oxygen deficit delta is increased from zero to 1 with x=0. For the case of Pr substitution, the drop in T(sub c) is believed due to magnetic interactions. For the case of varying delta with x=0, the drop can be attributed to a combination of magnetic interactions, band filling, and changes in crystal structure. To study these effects, the Mossbauer effect of 57 Fe atoms substituted for the Cu atoms has been observed as a function of delta, x, and temperature. The observed spectra are all well described by a two quadrupole-split pairs, a central singlet, and a six-line magnetic hyperfine field pattern. For several Pr compositions both delta and temperature were varied, and the results support the hypothesis that a magnetic interaction exists between the Fe in the Cu lattice and the substitutional Pr atoms.

  6. Spinel Ferrite Core-Shell Nanostructures by a Versatile Solvothermal Seed-Mediated Growth Approach and Study of Their Nanointerfaces.

    PubMed

    Sanna Angotzi, Marco; Musinu, Anna; Mameli, Valentina; Ardu, Andrea; Cara, Claudio; Niznansky, Daniel; Xin, Huolin L; Cannas, Carla

    2017-08-22

    An easy, low-cost, repeatable seed-mediated growth approach in solvothermal condition has been proposed to synthesize bimagnetic spinel ferrite core-shell heterostructures in the 10-20 nm particle size range. Cobalt ferrite and manganese ferrite nanoparticles (CoFe2O4 and MnFe2O4) have been coated with isostructural spinel ferrites like maghemite/magnetite, MnFe2O4, and CoFe2O4 with similar cell parameters to create different heterostructures. The conventional study of the structure, morphology, and composition has been combined with advanced techniques in order to achieve details on the interface at the nanoscale level. Clear evidence of the heterostructure formation have been obtained (i) indirectly by comparing the (57)Fe Mössbauer spectra of the core-shell samples and an ad hoc mechanical mixture and (ii) directly by mapping the nanoparticles' chemical composition by electron energy loss spectroscopy (EELS) and energy-dispersive X-ray spectroscopy (EDX) in the scanning transmission electron microscopy mode (STEM). In addition, chemical-sensitive electron tomography in STEM-EDX mode has been applied in order to obtain detailed 3D images with a sub-nanometer spatial resolution.

  7. A high spatial resolution synchrotron Mössbauer study of the Tazewell IIICD and Esquel pallasite meteorites.

    PubMed

    Blukis, Roberts; Rüffer, Rudolf; Chumakov, Aleksandr I; Harrison, Richard J

    2017-05-01

    Metallic phases in the Tazewell IIICD iron and Esquel pallasite meteorites were examined using (57)Fe synchrotron Mössbauer spectroscopy. Spatial resolution of ~10-20 μm was achieved, together with high throughput, enabling individual spectra to be recorded in less than 1 h. Spectra were recorded every 5-10 μm, allowing phase fractions and hyperfine parameters to be traced along transects of key microstructural features. The main focus of the study was the transitional region between kamacite and plessite, known as the "cloudy zone." Results confirm the presence of tetrataenite and antitaenite in the cloudy zone as its only components. However, both phases were also found in plessite, indicating that antitaenite is not restricted exclusively to the cloudy zone, as previously thought. The confirmation of paramagnetic antitaenite as the matrix phase of the cloudy zone contrasts with recent observations of a ferromagnetic matrix phase using X-ray photoemission electron spectroscopy. Possible explanations for the different results seen using these techniques are proposed.

  8. Mo¨ssbauer study of some archaeological materials in Tamilnadu (India)

    NASA Astrophysics Data System (ADS)

    Ramaswamy, K.; Dheenathayalu, M.; Barathan, S.

    1989-09-01

    57Fe Mo¨ssbauer absorption spectra have been recorded for archaeological pottery obtained from the excavated sites of Tamilnadu, namely, Gangaikondacholapuram, Kambanmedu, Melsathamangalam, Guttur, Uraiyur, Vallam and Kanchipuram. An attempt has been made to correlate the Mo¨ssbauer parameters with the oxidation states of iron, the colour, the temperature of firing and provenance.

  9. Forming the phosphate layer in reconstituted horse spleen ferritin and the role of phosphate in promoting core surface redox reactions.

    PubMed

    Johnson, J L; Cannon, M; Watt, R K; Frankel, R B; Watt, G D

    1999-05-18

    Apo horse spleen ferritin (apo HoSF) was reconstituted to various core sizes (100-3500 Fe3+/HoSF) by depositing Fe(OH)3 within the hollow HoSF interior by air oxidation of Fe2+. Fe2+ and phosphate (Pi) were then added anaerobically at a 1:4 ratio, and both Fe2+ and Pi were incorporated into the HoSF cores. The resulting Pi layer consisted of Fe2+ and Pi at about a 1:3 ratio which is strongly attached to the reconstituted ferritin mineral core surface and is stable even after air oxidation of the bound Fe2+. The total amount of Fe2+ and Pi bound to the iron core surface increases as the core volume increases up to a maximum near 2500 iron atoms, above which the size of the Pi layer decreases with increasing core size. Mössbauer spectroscopic measurements of the Pi-reconstituted HoSF cores using 57Fe2+ show that 57Fe3+ is the major species present under anaerobic conditions. This result suggests that the incoming 57Fe2+ undergoes an internal redox reaction to form 57Fe3+ during the formation of the Pi layer. Addition of bipyridine removes the 57Fe3+ bound in the Pi layer as [57Fe(bipy)3]2+, showing that the bound 57Fe2+ has not undergone irreversible oxidation. This result is related to previous studies showing that 57Fe2+ bound to native core is reversibly oxidized under anaerobic conditions in native holo bacterial and HoSF ferritins. Attempts to bury the Pi layer of native or reconstituted HoSF by adding 1000 additional iron atoms were not successful, suggesting that after its formation, the Pi layer "floats" on the developing iron mineral core.

  10. Mössbauer and Neutron Scattering Studies of Magnetic Properties of Random Mixtures with Competing Spin Anisotropies: FexCo1-xTiO3

    NASA Astrophysics Data System (ADS)

    Ito, Atsuko; Morimoto, Setsu; Someya, Yoshiko; Syono, Yasuhiko; Takei, Humihiko

    1982-10-01

    The physics of random mixtures with competing spin anisotropies is found to be much more complex than ever considered. According to our neutron scattering study of FexCo1-xTiO3, orderings of the orthogonal spin components S// and \\includegraphics{dummy.eps} seem to be decoupled with each other though not complete; two antiferromagnetic (AF) phases and a mixed ordering phase appear on the concentration vs temperature phase diagram. However, according to our Mössbauer study, S// and \\includegraphics{dummy.eps} seem to be closely coupled in the AF phases; the boundary between the AF and the mixed ordering phase is not found. This apparently contradictory result is interpreted as follows. In the \\includegraphics{dummy.eps} ordered AF phase, orientational distribution of \\includegraphics{dummy.eps} is such that it does not produce coherent scatterings of neutrons, but each \\includegraphics{dummy.eps} stays statically at least in the time scale of the Larmor precession time τL of 57Fe.

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

    PubMed

    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

    2015-08-10

    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 (57)Fe-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)(57)Fe plane was studied using (57)Fe-specific nuclear resonance vibrational spectroscopy and density functional theory (DFT) calculations. On Ni(μ-D)(57)Fe deuteride substitution, this wagging causes a characteristic perturbation of Fe-CO/CN bands. Spectra have been interpreted by comparison with Ni(μ-H/D)(57)Fe enzyme mimics [(dppe)Ni(μ-pdt)(μ-H/D)(57)Fe(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.

  12. 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.

  13. 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

  14. 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.

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

    DOE PAGES

    Ogata, Hideaki; Krämer, Tobias; Wang, Hongxin; ...

    2015-08-10

    The metabolism of many anaerobes relies on [NiFe]-hydrogenases, whose characterization when bound to substrates has proven non-trivial. Presented here is direct evidence for a hydride bridge in the active site of the 57Fe-labelled fully reduced Ni-R form of Desulfovibrio vulgaris Miyazaki F [NiFe]-hydrogenase. A unique ‘wagging’ mode involving H- motion perpendicular to the Ni(μ-H)57Fe plane was studied using 57Fe-specific nuclear resonance vibrational spectroscopy and density functional theory (DFT) calculations. On Ni(μ-D)57Fe deuteride substitution, this wagging causes a characteristic perturbation of Fe–CO/CN bands. Spectra have been interpreted by comparison with Ni(μ-H/D)57Fe enzyme mimics [(dppe)Ni(μ-pdt)(μ-H/D)57Fe(CO)3]+ and DFT calculations, which collectively indicate amore » low-spin Ni(II)(μ-H)Fe(II) core for Ni-R, with H- binding Ni more tightly than Fe. Lastly, the present methodology is also relevant to characterizing Fe–H moieties in other important natural and synthetic catalysts.« less

  16. Crystal structure, electronic and magnetic properties of double perovskite Ba2FeWO6: A combined experimental-theoretical study

    NASA Astrophysics Data System (ADS)

    Saad, H.-E, M. Musa; Rammeh, N.

    2016-01-01

    Double perovskite oxide Ba2FeWO6 has been synthesized in polycrystalline form by the solid-state ceramic method at 950 °C. Structural characterization was performed by using the X-ray powder diffraction (XRD) and neutron powder diffraction (NPD) followed by Rietveld analysis of these patterns. The crystal structure of Ba2FeWO6 is cubic; space group Fm-3m with lattice parameter of a=8.1351 Å. Also, a density functional theory (DFT) study of the crystal structure, electronic and magnetic properties of Ba2FeWO6 has been carried out using full potential linear muffin-tin orbital (FP-LMTO). We showed that the obtained symmetry lattice parameter agree well with the experimental results. The influence of Fe element on the magnetic and electronic properties of double perovskite oxide Ba2FeWO6 is analyzed. Band structure calculations for cubic Ba2FeWO6 predict an energy-gap in both spin-up and spin-down. The semiconductor antiferromagnetic (AFM) phase is stabilized by the hybridization of nonmagnetic W6+ (5d°) site positioned in between the magnetic Fe2+ (3d6) sites through the O2- anions in a long range O-Fe-O-W-O arrangement. 57Fe Mössbaur spectrum and DFT calculations suggest that the AFM behavior arises since the mixed valence Fe2+-Fe3+ effect introduces in Fe2+-O2--W6+ anticoupling.

  17. Comparative study of the microstructural and magnetic properties of fly ashes obtained from different thermal power plants in West Bengal, India.

    PubMed

    Bhattacharjee, Ashis; Mandal, Haradhan; Roy, Madhusudan; Kusz, Joachim; Hofmeister, Wolfgang

    2013-10-01

    This paper deals with the physical nature of the fly ashes obtained from two thermal power plants, situated in West Bengal, India. The fly ash samples are characterized by using comprehensive techniques with an emphasis on their ultrafine nature. The particle sizes of the samples are estimated using scanning electron microcopy (SEM) and found to lie within 0.18-5.90 μm. For morphology and compositional analysis, we also use SEM coupled with energy dispersive X-ray spectrometry. From X-ray study of the fly ashes the nature of conglomeration is seen to be crystalline, and the major components are mullite (Al6Si2O13) and quartz (SiO2). The magnetic measurement of the fly ash samples was carried out by SQUID magnetometer. (57)Fe Mössbauer spectra are obtained using a conventional constant-acceleration spectrometer with a (57)Co/Rh Mössbauer source. The hyperfine parameters obtained, in general, support the findings as made from XRD analysis and provide a quantitative measure of different iron ions present in the samples. The paper presents experimental data on the physical aspects of the fly ash samples of the thermal power plants which comprise coarse, fine, and ultrafine magnetic particulate materials and attempts to provide an exhaustive analysis.

  18. Mössbauer and XRD study of pulse plated Sn-Fe, Sn-Ni and Sn-Ni-Fe electrodeposited alloys

    NASA Astrophysics Data System (ADS)

    Stichleutner, S.; Lak, G. B.; Kuzmann, E.; Chisholm, C. U.; El-Sharif, M.; Homonnay, Z.; Sziráki, L.

    2014-04-01

    Effect of pulse plating on novel electrodeposited binary and ternary amorphous alloys was studied by 57Fe and 119Sn conversion electron Mössbauer spectroscopy and X-ray diffraction. Our results show that by adjusting the parameters of pulse plating a fine tuning of the composition and current efficiency can be achieved within these systems. On the contrary to direct current deposition, where the crystalline FeSn2 phase dominates, pulse plating technique produces amorphous Sn-Fe alloy phases, of which the ferromagnetic phase is the dominant one. Both, direct current and pulse plated Sn-Ni deposits consist of paramagnetic alloy phases and minor amounts of β-Sn, the occurrence of which correlates with the tin content of the samples. Pulse plated Sn-Ni-Fe coatings are amorphous and in a dominantly ferromagnetic state, however at long on- and off-pulse times and high peak current density the paramagnetic state dominates and β-Sn segregation also occurs.

  19. Magnetic composites from minerals: study of the iron phases in clay and diatomite using Mössbauer spectroscopy, magnetic measurements and XRD

    NASA Astrophysics Data System (ADS)

    Cabrera, M.; Maciel, J. C.; Quispe-Marcatoma, J.; Pandey, B.; Neri, D. F. M.; Soria, F.; Baggio-Saitovitch, E.; de Carvalho, L. B.

    2014-01-01

    Magnetic particles as matrix for enzyme immobilization have been used and due to the enzymatic derivative can be easily removed from the reaction mixture by a magnetic field. This work presents a study about the synthesis and characterization of iron phases into magnetic montmorillonite clay (mMMT) and magnetic diatomaceous earth (mDE) by 57Fe Mössbauer spectroscopy (MS), magnetic measurements and X-ray diffraction (XRD). Also these magnetic materials were assessed as matrices for the immobilization of invertase via covalent binding. Mössbauer spectra of the magnetic composites performed at 4.2 K showed a mixture of magnetite and maghemite about equal proportion in the mMMT, and a pure magnetite phase in the sample mDE. These results were verified using XRD. The residual specific activity of the immobilized invertase on mMMT and mDE were 83 % and 92.5 %, respectively. Thus, both magnetic composites showed to be promising matrices for covalent immobilization of invertase.

  20. Determination of manganese-53 by neutron activation and other miscellaneous studies on lunar dust.

    PubMed

    Herr, W; Herpers, U; Hess, B; Skerra, B; Woelfle, R

    1970-01-30

    A highly sensitive determination of spallogenic (53)Mn (T = 2 x 106 yr) was accomplished in 0.99 g of lunar soil. The chemical yield of Mn is determined with "carrier-free" (52)Mn tracer. During a 23-day reactor irradiation the (53)Mn is transformed into (54)Mn (T = 300 days). Appropriate chemical recycling was done by ion exchange and distillation. Interferences of the (n,p) and the (n,2n) nuclear reactions were carefully studied. A (53)Mn disintegration rate of 30.3 +/- 5.5 dpm/kg results. This extremely economic method is proposed for further detailed lunar profile measurements. The Re content, which is of possible cosmochemical interest, was determined to be 11 ppb. Appropriate separation techniques were used. The rather weak and complex thermoluminescence properties made a more basic study advisable. Thermogravimetric analysis, mass spectroscopy, and Moessbauer spectroscopy were applied. The presence of ilmenite, metallic Fe etc., and of an unidentified Fe(2+)-containing compound was deduced. Natural thermoluminescence could not be proved with certainty in our surface sample. However, the complexity of the artificial thermoluminescence demands better defined mineral fractions. The fission track method was used to measure U distribution in glass spherules etc.

  1. MAGNETO-CHEMICAL CHARACTER STUDIES OF NOVEL FE CATALYSTS FOR COAL LIQUEFACTION

    SciTech Connect

    Murty A. Akundi

    1997-10-01

    Co-precipitation is the major method proposed for synthesis of molybdenum oxide supported Fe, Fe/Co, and Fe/Cu catalysts. However, many variables may effect the particle size and surface properties of the synthesized catalysts, such as pH of molybdate solution, precipitation temperature and pH, Fe/Mo atomic ratio, pH of the washing solution, aging of the freshly prepared samples, and the length and temperature of calcination. In this period, we have been working on precipitation between iron(III) nitrate solution and ammonium para-molybdate solution under controlled pH condition, and with different Me/Fe atomic ratio. The effect of aging time on the property of the samples was also studied. The samples with the ratio of Fe/MoO{sub 3}: 6.5%, 20%, 26%, and 30% were prepared using above mentioned method. The samples with 6.5% and 26% were characterized with thermal analysis, infrared spectroscopy, magnetization, Moessbauer and X-ray diffraction before and after calcination at 400 C. FTIR was examined on precipitate, calacined and reduced samples as well as CO adsorbed and desorbed samples. Magnetization Studies were made on precipitated, calacined, and reduced samples. Their synthesis and characterization are presented in this report.

  2. Structural study and physical properties of a new phosphate KCuFe(PO{sub 4}){sub 2}

    SciTech Connect

    Badri, Abdessalem; Hidouri, Mourad; Lopez, Maria Luisa; Pico, Carlos; Wattiaux, Alain; Ben Amara, Mongi

    2011-04-15

    Single crystals of a new phosphate KCuFe(PO{sub 4}){sub 2} have been prepared by the flux method and its structural and physical properties have been investigated. This compound crystallizes in the monoclinic system with the space group P2{sub 1}/n and its parameters are: a=7.958(3) A, b=9.931(2) A, c=9.039(2) A, {beta}=115.59(3){sup o} and Z=4. Its structure consists of FeO{sub 6} octahedra sharing corners with Cu{sub 2}O{sub 8} units of edge-sharing CuO{sub 5} polyhedra to form undulating chains extending infinitely along the b-axis. These chains are connected by the phosphate tetrahedra giving rise to a 3D framework with six-sided tunnels parallel to the [101] direction, where the K{sup +} ions are located. The Moessbauer spectroscopy results confirm the exclusive presence of octahedral Fe{sup 3+} ions. The magnetic measurements show the compound to be antiferromagnetic with C{sub m}=5.71 emu K/mol and {theta}=-156.5 K. The derived experimental effective moment {mu}{sub ex}=6.76{mu}{sub B} is somewhat higher than the theoretical one of {mu}{sub th}=6.16{mu}{sub B}, calculated taking only into account the spin contribution for Fe{sup 3+} and Cu{sup 2+} cations. Electrical measurements allow us to obtain the activation energy (1.22 eV) and the conductivity measurements suggest that the charge carriers through the structure are the potassium cations. -- Graphical abstract: A projection along the [101] direction of the structure showing the six-edged tunnels, occupied by the K{sup +} ions. Display Omitted Highlights: {yields} The reported structure is of a new type. {yields} The structural model is supported by a Moessbauer spectroscopy study. {yields} The magnetic susceptibility results are reported. {yields} The electrical properties are discussed.

  3. Iron isotope effect in SmFeAsO0.65 and SmFeAsO0.77H0.12 superconductors: A Raman study

    NASA Astrophysics Data System (ADS)

    Singh, Birender; Shirage, P. M.; Iyo, A.; Kumar, Pradeep

    2016-10-01

    We report the inelastic light scattering studies on SmFeAsO0.65 and SmFeAsO0.77H0.12 with iron isotopes namely 54Fe and 57Fe. In both of these systems under investigation we observed a significant shift in the frequency of the phonon modes associated with the displacement of Fe atoms around ˜ 200 cm-1. The observed shift in the Fe mode (B1g) for SmFeAsO0.65 is ˜ 1.4 % and lower in case of SmFeAsO0.77H0.12, which is ˜ 0.65 %, attributed to the lower percentage of isotopic substitution in case of SmFeAsO0.77H0.12. Our study reveals the significant iron isotope effect in these systems hinting towards the crucial role of electron-phonon coupling in the pairing mechanism of iron based superconductors.

  4. Effects of time and temperature of firing on Fe-rich ceramics studied by Mössbauer spectroscopy and two-dimensional 1H-nuclear magnetic resonance relaxometry

    NASA Astrophysics Data System (ADS)

    Casieri, Cinzia; De Luca, Francesco; Nodari, Luca; Russo, Umberto; Terenzi, Camilla; Tudisca, Valentina

    2012-10-01

    The combined effects of firing temperature and soaking time on the microstructure of iron-rich porous ceramics have been studied by 57Fe-Mössbauer spectroscopy and 2D 1H nuclear magnetic resonance (NMR) relaxometry using a single-sided probe. Examining water-saturated ceramics using the relaxation correlation method, where longitudinal (T1) and transverse (T2) relaxation times are measured concurrently, provides information about firing-induced changes in both porosity (related to T1) and magnetic properties (related to T2). Comparing the information obtained from 1H-NMR analyses with that obtained from Mössbauer spectroscopy (which characterizes changes in iron-bearing species) shows that the T1-T2 NMR correlation technique is very sensitive to even subtle modifications in the magnetic behavior of Fe-bearing species. Moreover, the single-sided NMR approach allows us to perform millimeter-scale depth-resolved measurements, which can be used to non-invasively study the microstructural heterogeneities associated with non-uniform firing effects inside ceramics. This is in contrast to Mössbauer spectroscopy, which requires that the ceramic samples be ground.

  5. Influence of pH, iron source, and Fe/ligand ratio on iron speciation in lignosulfonate complexes studied using Mössbauer spectroscopy. Implications on their fertilizer properties.

    PubMed

    Carrasco, Jaime; Kovács, Krisztina; Czech, Viktória; Fodor, Ferenc; Lucena, Juan J; Vértes, Attila; Hernández-Apaolaza, Lourdes

    2012-04-04

    Iron chlorosis is a very common nutritional disorder in plants that can be treated using iron fertilizers. Synthetic chelates have been used to correct this problem, but nowadays environmental concerns have enforced the search for new, more environmentally friendly ligands, such as lignosulfonates. In this paper, Fe coordination environment and speciation in lignosulfonate (LS) complexes prepared under different experimental conditions were studied by (57)Fe Mössbauer spectroscopy in relation to the Fe-complexing capacities, chemical characteristics of the different products, and efficiency to provide iron in agronomic conditions. It has been observed that the complex formation between iron and lignosulfonates involves different coordination sites. When Fe(2+) is used to prepare the iron-LS product, complexes form weak adducts and are sensitive to oxidation, especially at neutral or alkaline pH. However, when Fe(3+) is used to form the complexes, both Fe(2+) and Fe(3+) are found. Reductive sugars, normally present in lignosulfonates, favor a relatively high content of Fe(2+) even in those complexes prepared using Fe(3+). The formation of amorphous ferrihydrite is also possible. With respect to the agronomical relevance of the Fe(2+)/Fe(3+) speciation provided by the Mössbauer spectra, it seems that the strong Fe(3+)-LS complexes are preferred when they are applied to the leaf, whereas root uptake in hydroponics could be more related with the presence of weak bonding sites.

  6. Synthesis of α-Fe{sub 2}O{sub 3}-functionalised graphene oxide nanocomposite by a facile low temperature method and study of its magnetic and hyperfine properties

    SciTech Connect

    Nag, Sanchayita; Roychowdhury, Anirban; Das, Dipankar

    2016-02-15

    Highlights: • Synthesis of reduced graphene oxide (rGO)/α-Fe{sub 2}O{sub 3} nanocomposites (NCs) by sol–gel method. • Samples exhibited ferromagnetism originated due to surface canted spins. • rGO enhanced the value of saturation magnetization and coercivity of the bare nanoparticle. • RKKY coupling between the isolated rGO spins and the magnetic nanoparticles. - Abstract: Reduced graphene oxide/α-Fe{sub 2}O{sub 3} nanocomposites were synthesized by a simple sol–gel method. Initially, the samples were investigated by X-ray diffraction, high resolution transmission electron microscopy and Raman spectroscopy. High resolution transmission electron micrographs indicate that the magnetic nanoparticles are well dispersed in the reduced graphene oxide sheet-like structure. Fourier transform infrared spectroscopy studies corroborate the results obtained by X-ray diffraction. Temperature as well as field dependent magnetic measurements revealed ferromagnetism in the pristine α-Fe{sub 2}O{sub 3} as well as in the nanocomposite sample that is attributed to surface canted spins and defects present in the samples. The enhanced value of coercivity in case of the nanocomposite sample could be ascribed to the Ruderman–Kittel–Kasuya–Yosida type of interaction between the isolated reduced graphene oxide spin and the magnetic ions. Presence of super paramagnetic doublet as well as sextet patterns related to hematite phase is confirmed by the {sup 57}Fe-Mössbauer spectroscopy.

  7. Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes

    DOE PAGES

    Bucinsky, Lukas; Breza, Martin; Lee, Wei-Tsung; ...

    2017-04-05

    High-oxidation state metal complexes with multiply bonded ligands are of great interest for both their reactivity as well as their fundamental bonding properties. This paper reports a combined spectroscopic and theoretical investigation into the effect of the apical multiply bonded ligand on the spin state preferences of three-fold symmetric iron(IV) complexes with tris(carbene) donor ligands. Specifically, singlet (S = 0) nitrido [{PhB(ImR)3}FeN], R = tBu (1), Mes (mesityl, 2) and the related triplet (S = 1) imido complexes, [{PhB(ImR)3}Fe(NR')]+, R = Mes, R' = Ad (1- adamantyl, 3), tBu (4), have been investigated by electronic absorption and Mössbauer effect spectroscopies.more » For comparison, two other Fe(IV) nitrido complexes, [(TIMENAr)FeN]+, (TIMENAr = tris[2-(3-aryl-imidazol-2-ylidene)ethyl]amine; Ar = Xyl (xylyl), Mes), have been investigated by 57Fe Mössbauer spectroscopy, including applied-field measurements. The paramagnetic imido complexes 3 and 4 were also studied by magnetic susceptibility measurements (for 3) and paramagnetic resonance spectroscopy: high-frequency and -field electron paramagnetic resonance (HFEPR) (for 3 and 4) and frequency-domain Fouriertransform (FD-FT) THz EPR (for 3), which reveal their zero-field splitting (zfs) parameters. Experimentally correlated theoretical studies comprising ligand-field theory (LFT) and quantum chemical theory (QCT), the latter including both density functional theory (DFT) and ab initio methods reveal the key role played by the Fe3dz2 (a1) orbital in these systems: the nature of its interaction with the nitrido or imido ligand dictates the spin state preference of the complex. Lastly, the ability to tune the spin state through the energy and nature of a single orbital has general relevance to the factors controlling spin states in complexes with applicability as single molecule devices.« less

  8. Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes.

    PubMed

    Bucinsky, Lukas; Breza, Martin; Lee, Wei-Tsung; Hickey, Anne K; Dickie, Diane A; Nieto, Ismael; DeGayner, Jordan A; Harris, T David; Meyer, Karsten; Krzystek, J; Ozarowski, Andrew; Nehrkorn, Joscha; Schnegg, Alexander; Holldack, Karsten; Herber, Rolfe H; Telser, Joshua; Smith, Jeremy M

    2017-04-05

    High-oxidation-state metal complexes with multiply bonded ligands are of great interest for both their reactivity as well as their fundamental bonding properties. This paper reports a combined spectroscopic and theoretical investigation into the effect of the apical multiply bonded ligand on the spin-state preferences of threefold symmetric iron(IV) complexes with tris(carbene) donor ligands. Specifically, singlet (S = 0) nitrido [{PhB(Im(R))3}FeN], R = (t)Bu (1), Mes (mesityl, 2) and the related triplet (S = 1) imido complexes, [{PhB(Im(R))3}Fe(NR')](+), R = Mes, R' = 1-adamantyl (3), (t)Bu (4), were investigated by electronic absorption and Mössbauer effect spectroscopies. For comparison, two other Fe(IV) nitrido complexes, [(TIMEN(Ar))FeN](+) (TIMEN(Ar) = tris[2-(3-aryl-imidazol-2-ylidene)ethyl]amine; Ar = Xyl (xylyl), Mes), were investigated by (57)Fe Mössbauer spectroscopy, including applied-field measurements. The paramagnetic imido complexes 3 and 4 were also studied by magnetic susceptibility measurements (for 3) and paramagnetic resonance spectroscopy: high-frequency and -field electron paramagnetic resonance (for 3 and 4) and frequency-domain Fourier-transform (FD-FT) terahertz electron paramagnetic resonance (for 3), which reveal their zero-field splitting parameters. Experimentally correlated theoretical studies comprising ligand-field theory and quantum chemical theory, the latter including both density functional theory and ab initio methods, reveal the key role played by the Fe 3dz(2) (a1) orbital in these systems: the nature of its interaction with the nitrido or imido ligand dictates the spin-state preference of the complex. The ability to tune the spin state through the energy and nature of a single orbital has general relevance to the factors controlling spin states in complexes with applicability as single molecule devices.

  9. Mössbauer and XRD studies of Roman amphorae buried in the sea for two millennia

    NASA Astrophysics Data System (ADS)

    Wagner, F. E.; Wagner, U.; Häusler, W.; Costa, B. F. O.; Blot, J.-Y.; Silva, A. J. M.; Bombico, S.

    2016-12-01

    During the years 2004-2007 many Roman amphora sherds were found in the sea near Cortiçais, off the southern coast of the Peniche peninsula on the Atlantic coast of Portugal. The amphorae are of the Haltern 70 type and stem from a shipwreck that has been dated to the time of the emperor Augustus, between about 15 BC and 15 AD. They were produced in the Roman Province of Baetica in the south of Spain and used to transport wine and other staple foods by sea to other Roman settlements. We have studied several fragments of these amphorae by 57Fe Mössbauer spectroscopy and X-ray diffraction in order to look for changes in the ceramic material caused by two millennia of exposure to sea water. For comparison Mössbauer data on a Haltern 70 type amphora handle excavated on land at the site of Castro do Vieito in the north of Portugal were used. The fragments on which we report here are a body sherd and two handles. The sherds show a visible layer structure. The different layers were studied separately. The Mössbauer spectra of the buff surface layers indicate that up to about 60 % of the iron is present as very fine goethite particles, which are superparamagnetic at RT but exhibit magnetically split spectra at 4.2 K. Their blocking temperature is around or even below 50 K. The goethite is too fine grained to be detected by X-ray diffraction. Re-firing experiments confirm the presence of goethite, which is found to convert to hematite between 300 and 600 ∘C. The results show that the iron in the silicate matrix of the ceramic material converts to goethite under the prolonged influence of the sea water, mainly in the outermost several millimetres and apparently depending on the nature of the ceramic material.

  10. Structure and magnetic properties of the cubic oxide fluoride BaFeO{sub 2}F

    SciTech Connect

    Berry, Frank J.; Coomer, Fiona C.; Hancock, Cathryn; Helgason, Orn; Moore, Elaine A.; Slater, Peter R.; Wright, Adrian J.; Thomas, Michael F.

    2011-06-15

    Fluorination of the parent oxide, BaFeO{sub 3-{delta}}, with polyvinylidine fluoride gives rise to a cubic compound with a=4.0603(4) A at 298 K. {sup 57}Fe Moessbauer spectra confirmed that all the iron is present as Fe{sup 3+}. Neutron diffraction data showed complete occupancy of the anion sites, indicating a composition BaFeO{sub 2}F, with a large displacement of the iron off-site. The magnetic ordering temperature was determined as T{sub N}=645{+-}5 K. Neutron diffraction data at 4.2 K established G-type antiferromagnetism with a magnetic moment per Fe{sup 3+} ion of 3.95 {mu}{sub B}. However, magnetisation measurements indicated the presence of a weak ferromagnetic moment that is assigned to the canting of the antiferromagnetic structure. {sup 57}Fe Moessbauer spectra in the temperature range 10-300 K were fitted with a model of fluoride ion distribution that retains charge neutrality of the perovskite unit cell. - Graphical abstract: The cubic oxide fluoride of composition BaFeO{sub 2}F has been synthesised and characterised. Highlights: > Fluorination of BaFeO{sub 3-{delta}} with polyvinylidene fluoride gives a cubic oxide fluoride of composition BaFeO{sub 2}F. > BaFeO{sub 2}F adopts a canted antiferromagnetic structure and is different from the related phase of composition SrFeO{sub 2}F. > A model of fluoride ion distribution about iron in BaFeO{sub 2}F has been explored.

  11. Crystal chemical constraints on inter-mineral Fe isotope fractionation and implications for Fe isotope disequilibrium in San Carlos mantle xenoliths

    NASA Astrophysics Data System (ADS)

    Macris, Catherine A.; Manning, Craig E.; Young, Edward D.

    2015-04-01

    The origin of variations in iron isotope compositions of mantle minerals is uncertain, and predictions of equilibrium inter-mineral iron isotope fractionation conflict. This hinders interpretation of the petrologic and geochemical implications of Fe isotope data from mantle lithologies. To address this, we present a revised ionic model for predicting equilibrium iron isotope fractionation between mantle minerals and use it to interpret measured inter-mineral iron isotopic fractionation from five distinct mantle xenolith lithologies from San Carlos, Arizona. The samples represent a broad range of modal abundances and include lherzolite, harzburgite, dunite, clinopyroxenite, and websterite. The xenoliths exhibit Fe-isotopic variation between minerals in a single sample, and between samples. In all cases where spinel and olivine coexist, the 57Fe/54Fe of spinel is greater than that of the corresponding olivine, agreeing with expectations for equilibrium fractionation from theory (ionic model), but disagreeing with predictions based on Mössbauer data. The 57Fe/54Fe values of clinopyroxenes from the xenoliths show no clear systematic differences. We interpret this to be a result of varying degrees of metasomatism, perhaps involving interaction with a melt. The spinel peridotite samples (lherzolite, harzburgite, and dunite) are partially melted residual mantle that exhibit a decrease in whole-rock 57Fe/54Fe with increasing olivine abundance. This is consistent with progressive extraction of a 57Fe-rich partial melt. The clinopyroxenite has the highest whole-rock 57Fe/54Fe, consistent with its origin as a cumulate from an unrelated magma possessing elevated 57Fe/54Fe. The websterite sample is transitional to Group II type xenoliths, has the lowest whole-rock 57Fe/54Fe of the investigated samples, and likely experienced a more complex metasomatic history. This study demonstrates that the Fe isotope compositions of San Carlos xenoliths and their component minerals record

  12. The Study of Kinetics of Diffusion and Phase Formation in the Layered Iron-Beryllium System

    NASA Astrophysics Data System (ADS)

    Kuterbekov, K. A.; Nurkenov, S. A.; Kislitsin, S. B.; Kuketayev, T. A.; Nurakhmetov, T. N.

    2017-02-01

    The methods of Mössbauer spectroscopy with X-ray phase analysis and Rutherford backscattering of protons were used to study the kinetics of diffusion and phase transformations in the layered iron-beryllium system. For the first time, the authors suggested and implemented a method for retardation of diffusion and phase formation processes in the layered iron-beryllium system using the barrier layer. It was established that the barrier layer limits the zone of beryllium dissolution in the area of implanted layer. The impact of the barrier layer on kinetics of thermally induced processes of diffusion and phase transformations in the layered Fe-Be system was determined using the example of Fe (10 μm): O+ - Be (0.7 μm) - 57Fe (0.1 μm). The authors suggested and implemented a method for recovery of the distribution function of the admixture atom concentration in the solid matrix-admixture solution on the basis of the X-ray diffraction data. The kinetics of mutual diffusion was determined for Fe and Be atoms in the α-Fe(Be) solution for both sides of the layered systems with a barrier layer and without it using the suggested method for recovery of the distribution function of the Be atom concentration. It was established that for the system without a barrier layer, the share of iron atoms ends at tann 5 h on the coating side and at tann 7.5 h on the iron side, while for the barrier layer case - at tann 20 h on the coating side and at tann 40 h on the iron side.

  13. Preparation and Characterization of Ultrathin Stainless Steel Films

    SciTech Connect

    Sahoo, B.; Schlage, K.; Roehlsberger, R.; Major, J.; Hoersten, U. von; Keune, W.; Wende, H.

    2011-06-30

    We report on the preparation of polycrystalline austenitic 310 ({sup 57}Fe{sub 0.55}Cr{sub 0.25}Ni{sub 0.20}) stainless steel (SS) thin films on Si substrates and the characterization of their residual magnetism via {sup 57}Fe conversion-electron Moessbauer spectroscopy (CEMS). The films were structurally characterized at room temperature by X-ray diffraction (XRD). The virgin films were found to be structurally disordered. Subsequent annealing at moderate temperatures in ultrahigh vacuum produces the ordered martensitic and austenitic SS phases. Further annealing at higher temperatures (up to temperatures where long-range diffusion into the substrate is still weak) transforms the films into the austenitic phase with no trace of a magnetic hyperfine interaction. However, when a 2 nm thick SS thin film is embedded between two carbon layers, the as prepared disordered SS film does not transform to the martensitic or austenitic SS phase irrespective of the annealing temperature, probably because the interdiffusion with C prohibits the formation of these phases.

  14. Magnetic and Mossbauer study of amorphous and nanocrystalline Fe[sub 86]Zr[sub 7]Cu[sub 1]B[sub 6] alloys

    SciTech Connect

    Gorria, P.; Orue, I.; Plazaola, F.; Fernandez-Gubieda, M.L.; Barandiaran, J.M. . Dept. de Electricidad y Electronica)

    1993-11-01

    Amorphous alloys of composition Fe[sub 86]Zr[sub 7]Cu[sub 1]B[sub 6] have been prepared and annealed in the temperature range from 570 to 950 K, obtaining several degrees of nanocrystallization. Magnetic and Moessbauer measurements show the different phases that appear in the samples after the heating, and their percentage, depending on the annealing temperature. The Curie temperature of the amorphous phase is shown to remain almost unchanged during the crystallization. Moessbauer spectroscopy however, reveals subtle changes in the structure.

  15. Atypical iron storage in marine brown algae: a multidisciplinary study of iron transport and storage in Ectocarpus siliculosus

    PubMed Central

    Matzanke, Berthold F.; Küpper, Frithjof C.; Carrano, Carl J.

    2012-01-01

    Iron is an essential element for all living organisms due to its ubiquitous role in redox and other enzymes, especially in the context of respiration and photosynthesis. The iron uptake and storage systems of terrestrial/higher plants are now reasonably well understood, with two basic strategies for iron uptake being distinguished: strategy I plants use a mechanism involving induction of Fe(III)-chelate reductase (ferrireductase) and Fe(II) transporter proteins, while strategy II plants utilize high-affinity, iron-specific, binding compounds called phytosiderophores. In contrast, little is known about the corresponding systems in marine, plant-like lineages, particularly those of multicellular algae (seaweeds). Herein the first study of the iron uptake and storage mechanisms in the brown alga Ectocarpus siliculosus is reported. Genomic data suggest that Ectocarpus may use a strategy I approach. Short-term radio-iron uptake studies verified that iron is taken up by Ectocarpus in a time- and concentration-dependent manner consistent with an active transport process. Upon long-term exposure to 57Fe, two metabolites have been identified using a combination of Mössbauer and X-ray absorption spectroscopies. These include an iron–sulphur cluster accounting for ~26% of the total intracellular iron pool and a second component with spectra typical of a polymeric (Fe3+O6) system with parameters similar to the amorphous phosphorus-rich mineral core of bacterial and plant ferritins. This iron metabolite accounts for ~74% of the cellular iron pool and suggests that Ectocarpus contains a non-ferritin but mineral-based iron storage pool. PMID:22945940

  16. Structural and magnetic properties of DyFe/sub 3/ hydrides

    SciTech Connect

    Niarchos, D; Viccaro, P J; Dunlap, B D; Shenoy, G K; Aldred, A T

    1980-01-01

    The ternary hydride phases, DyFe/sub 3/H/sub x/ with x = 1.7, 2.5, and 4.2 all retain the PuNi/sub 3/ rhombohedral structure of DyFe/sub 3/ with a maximum volume expansion of 18% for DyFe/sub 3/H/sub 4.2/. All phases show a preferential expansion parallel to the c/sub 0/ axis. From bulk magnetization measurements, the Dy-Fe spin compensation temperature is found to decrease linearly from 545/sup 0/K for DyFe/sub 3/ to 150/sup 0/K for DyFe/sub 3/H/sub 4.2/ with increasing volume of the hydride phases. The /sup 161/Dy Moessbauer results for the two Dy sites in the structure indicate a slight reduction occurs in free-ion moment found for DyFe/sub 3/ in all hydride phases. In addition, the /sup 57/Fe Moessbauer data show that the average Fe moment for the five inequivalent Fe sites increases with hydrogen concentration up to x = 2.5.

  17. The effects of fat loss after bariatric surgery on inflammation, serum hepcidin, and iron absorption: a prospective 6-mo iron stable isotope study.

    PubMed

    Cepeda-Lopez, Ana C; Allende-Labastida, Javier; Melse-Boonstra, Alida; Osendarp, Saskia Jm; Herter-Aeberli, Isabelle; Moretti, Diego; Rodriguez-Lastra, Ramiro; Gonzalez-Salazar, Francisco; Villalpando, Salvador; Zimmermann, Michael B

    2016-10-01

    Iron deficiency is common in obese subjects. This may be due to an increase in serum hepcidin and a decrease in iron absorption from adiposity-related inflammation. We evaluated whether weight and fat loss in obese subjects would decrease inflammation and serum hepcidin and thereby improve iron absorption. We performed a 6-mo prospective study in obese [body mass index (in kg/m(2)) ≥35 and <45] adults who had recently undergone laparoscopic sleeve gastrectomy. At 2 and 8 mo postsurgery, subjects consumed a test drink with 6 mg (57)Fe as ferrous sulfate and were intravenously infused with 100 μg (58)Fe as iron citrate. We then compared erythrocyte incorporation of iron isotopic labels, changes in body composition, iron status, hepcidin, and inflammation at each time point. Forty-three subjects were studied at baseline, and 38 completed the protocol (32 women and 6 men). After 6 mo, total body fat, interleukin IL-6, and hepcidin were significantly lower (all P < 0.005). In iron-deficient subjects (n = 17), geometric mean (95% CI) iron absorption increased by 28% [from 9.7% (6.5%, 14.6%) to 12.4% (7.7%, 20.1%); P = 0.03], whereas in iron-sufficient subjects (n = 21), absorption did not change [5.9% (4.0%, 8.6%) and 5.6% (3.9%, 8.2%); P = 0.81]. Adiposity-related inflammation is associated with a reduction in the normal upregulation of iron absorption in iron-deficient obese subjects, and this adverse effect may be ameliorated by fat loss. This protocol was approved by the ethics committees of Wageningen University, ETH Zurich, the University of Monterrey, and the Federal Commission for the Protection against Sanitary Risks, and registered at clinicaltrials.gov as NCT01347905. © 2016 American Society for Nutrition.

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

    NASA Astrophysics Data System (ADS)

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

    2017-08-01

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

  19. Dimeric Fe (II, III) complex of quinoneoxime as functional model of PAP enzyme: Mössbauer, magneto-structural and DNA cleavage studies

    NASA Astrophysics Data System (ADS)

    Salunke-Gawali, Sunita; Ahmed, Khursheed; Varret, François; Linares, Jorge; Zaware, Santosh; Date, Sadgopal; Rane, Sandhya

    2008-07-01

    Purple acid phosphatase, ( PAP), is known to contain dinuclear Fe2 + 2, + 3 site with characteristic Fe + 3 ← Tyr ligand to metal charge transfer in coordination. Phthiocoloxime (3-methyl-2-hydroxy-1,4-naphthoquinone-1-oxime) ligand L, mimics (His/Tyr) ligation with controlled and unique charge transfers resulting in valence tautomeric coordination with mixed valent diiron site in model compound Fe-1: [μ-OH-Fe2 + 2, + 3 ( o-NQCH3ox) ( o-NSQCH3ox)2 (CAT) H2O]. Fe-2: [Fe + 3( o-NQCH3ox) ( p-NQCH3ox)2]2 a molecularly associated dimer of phthiocoloxime synthesized for comparison of charge transfer. 57Fe Mössbauer studies was used to quantitize unusual valences due to ligand in dimeric Fe-1 and Fe-2 complexes which are supported by EPR and SQUID studies. 57Fe Mössbauer spectra for Fe-1 at 300 K indicates the presence of two quadrupole split asymmetric doublets due to the differences in local coordination geometries of [Fe + 3]A and [Fe + 2]B sites. The hyperfine interaction parameters are δ A = 0.152, (Δ E Q)A = 0.598 mm/s with overlapping doublet at δ B = 0.410 and (Δ E Q)B = 0.468 mm/s. Due to molecular association tendency of ligand, dimer Fe-2 possesses 100% Fe + 3(h.s.) hexacoordinated configuration with isomer shift δ = 0.408 mm/s. Slightly distorted octahedral symmetry created by NQCH3ox ligand surrounding Fe + 3(h.s.) state generates small field gradient indicated by quadrupole split Δ E Q = 0.213 mm/s. Decrease of isomer shifts together with variation of quadrupole splits with temperature in Fe-1 dimer compared to Fe-2 is result of charge transfers in [Fe2 + 2, + 3 SQ] complexes. EPR spectrum of Fe-1 shows two strong signals at g 1 = 4.17 and g 2 = 2.01 indicative of S = 3/2 spin state with an intermediate spin of Fe + 3(h.s.) configuration. SQUID data of χ _m^{corr} .T were best fitted by using HDVV spin pair model S = 2, 3/2 resulting in antiferromagnetic exchange ( J = -13.5 cm - 1 with an agreement factor of R = 1.89 × 10 - 5). The lower J

  20. Polarized neutron study of the magnetization density distribution within a CoFe/sub 2/O/sub 4/ colloidal particle (magnetization density in a colloidal CoFe/sub 2/O/sub 4/ crystallite)

    SciTech Connect

    Nunes, A.C.; Majkrzak, C.F.; Berkowitz, A.E.

    1983-01-01

    Magnetization and Moessbauer data suggest that a magnetically anomalous region exists within finely divided CoFe/sub 2/O/sub 4/ particles when coated with oleic acid. We have undertaken an x-ray and a polarized neutron powder diffraction study of these samples with and without the surfactant coating in an attempt to locate and characterize this anomalous zone. The shape of neutron scans of the (4,0,0) reflection are independent of polarization indicating that the reflecting crystallites are uniformly magnetized. Magnetization calculated from the peak flipping ratio is characteristic of uncoated rather than coated particles in both cases. Scan widths of both x-rays and neutrons are narrower for the sample from which the chemisorbed surfactant has been largely removed indicating an increase in the size of the coherent lattice of a crystallite. These observations are consistent with the existence of a highly strained surface layer roughly 10 Angstroms thick characterized by pinned spins associated with the presence of oleic acid, which relaxes to a more normal lattice structure upon boiling off the surfactant.

  1. The interaction of Fe on MgO(1 0 0) surfaces

    NASA Astrophysics Data System (ADS)

    Fetzer, Cs.; Dézsi, I.; Szűcs, I.; Tanczikó, F.; Balogh, A. G.

    2009-10-01

    The atomic interaction and magnetic properties of ultrathin Fe films grown on cleaved and polished MgO(1 0 0) surfaces were studied by conversion electron Mössbauer spectroscopy (CEMS). 57Fe layers were deposited as probe atoms in different layer positions in 10 ML thick Fe films. Fe layers of different thicknesses were formed on polished and cleaved substrate surfaces at RT deposition. The analysis of the spectra showed no Fe-O interaction in MgO/Fe interface. FeO phase formation was excluded. The Mössbauer spectrum of 5 ML 57Fe sample showed enhanced internal magnetic field at 80 K. No interdiffusion of 57Fe and 56Fe atoms was observed between the layers at room temperature.

  2. Chemical mixing at “Al on Fe” and “Fe on Al” interfaces

    SciTech Connect

    Süle, P.; Horváth, Z. E.; Kaptás, D.; Bujdosó, L.; Balogh, J.; Nakanishi, A.

    2015-10-07

    The chemical mixing at the “Al on Fe” and “Fe on Al” interfaces was studied by molecular dynamics simulations of the layer growth and by {sup 57}Fe Mössbauer spectroscopy. The concentration distribution along the layer growth direction was calculated for different crystallographic orientations, and atomically sharp “Al on Fe” interfaces were found when Al grows over (001) and (110) oriented Fe layers. The Al/Fe(111) interface is also narrow as compared to the intermixing found at the “Fe on Al” interfaces for any orientation. Conversion electron Mössbauer measurements of trilayers—Al/{sup 57}Fe/Al and Al/{sup 57}Fe/Ag grown simultaneously over Si(111) substrate by vacuum evaporation—support the results of the molecular dynamics calculations.

  3. Quantum cluster size and solvent polarity effects on the geometries and Mössbauer properties of the active site model for ribonucleotide reductase intermediate X: a density functional theory study.

    PubMed

    Han, Wen-Ge; Noodleman, Louis

    2010-03-01

    In studying the properties of metalloproteins using ab initio quantum mechanical methods, one has to focus on the calculations on the active site. The bulk protein and solvent environment is often neglected, or is treated as a continuum dielectric medium with a certain dielectric constant. The size of the quantum cluster of the active site chosen for calculations can vary by including only the first-shell ligands which are directly bound to the metal centers, or including also the second-shell residues which are adjacent to and normally have H-bonding interactions with the first-shell ligands, or by including also further hydrogen bonding residues. It is not well understood how the size of the quantum cluster and the value of the dielectric constant chosen for the calculations will influence the calculated properties. In this paper, we have studied three models (A, B, and C) of different sizes for the active site of the ribonucleotide reductase intermediate X, using density functional theory (DFT) OPBE functional with broken-symmetry methodology. Each model is studied in gas-phase and in the conductor-like screening (COSMO) solvation model with different dielectric constants ε = 4, 10, 20, and 80, respectively. All the calculated Fe-ligand geometries, Heisenberg J coupling constants, and the Mössbauer isomer shifts, quadrupole splittings, and the (57)Fe, (1)H, and (17)O hyperfine tensors are compared. We find that the calculated isomer shifts are very stable. They are virtually unchanged with respect to the size of the cluster and the dielectric constant of the environment. On the other hand, certain Fe-ligand distances are sensitive to both the size of the cluster and the value of ε. ε = 4, which is normally used for the protein environment, appears too small when studying the diiron active site geometry with only the first-shell ligands as seen by comparisons with larger models.

  4. Mineralogy of SNC Meteorite EET79001 by Simultaneous Fitting of Moessbauer Backscatter Spectra

    NASA Technical Reports Server (NTRS)

    Morris, Richard V.; Agresti, D. G.

    2010-01-01

    We have acquired M ssbauer spectra for SNC meteorite EET79001 with a MIMOS II backscatter M ssbauer spectrometer [1] similar to those now operating on Mars as part of the Mars Exploration Rover (MER) missions. We are working to compare the Fe mineralogical composition of martian meteorites with in-situ measurements on Mars. Our samples were hand picked from the >1 mm size fraction of saw fines on the basis of lithology, color, and grain size (Table 1). The chips were individually analyzed at approx.300K by placing them on a piece of plastic that was in turn supported by the contact ring of the instrument (oriented vertically). Tungsten foil was used to mask certain areas from analysis. As shown in Figure 1, a variety of spectra was obtained, each resulting from different relative contributions of the Fe-bearing minerals present in the sample. Because the nine samples are reasonably mixtures of the same Fe-bearing phases in variable proportions, the nine spectra were fit simultaneously (simfit) with a common model, adjusting parameters to a single minimum chi-squared convergence criterion [2]. The starting point for the fitting model and values of hyperfine parameters was the work of Solberg and Burns [3], who identified olivine, pyroxene, and ferrous glass as major, and ilmenite and a ferric phase as minor (<5%), Fe-bearing phases in EET79001.

  5. Behavioral response of pyrite structured Co0.2Fe0.8S2 nano-wires under high-pressure up to 8 GPa - Mössbauer spectroscopic and electrical resistivity studies

    NASA Astrophysics Data System (ADS)

    Chandra, U.; Sharma, P.; Parthasarathy, G.; Sreedhar, B.

    2016-02-01

    Pyrite-structured Co0.2Fe0.8S2 nano wires with aspect ratio 45:1, synthesized using solution colloid method were studied under high pressure up to 8 GPa using 57Fe Mössbauer spectroscopy (using diamond anvil cell) and electrical resistivity (using tungsten carbide cell) techniques. Room temperature S K-edge XANES studies at INFN-LNF synchrotron beam line signified the changes in the electronic structure owing to Co substitution. Magnetic measurements at 5 K demonstrated disordered ferromagnetic behavior similar to Griffith phase. The value of isomer shift identified Fe in divalent, low spin state corresponding to pyrite structure. Higher value of quadrupole splitting observed at ambient condition was due to large lattice strain and electric field gradient generated by large surface to volume ratio of the nano size of the system. With applied pressure, the value followed the expected trend of increase up to 4.3 GPa, then to decrease till 6.4 GPa. Such change in the trend suggested a phase transition. On decompression to ambient pressure, the system seemed to retain high pressure phase and nano structure. The pressure coefficient of electrical resistivity varying from -0.0454 to -0.166 Ω-cm/GPa across the transition pressure of ~4.5 GPa was sluggish suggesting second order phase transition. The pressure-dependent variations by Mössbauer parameters and electrical resistivity showed identical result. This is the first report of pressure effect on nano sized Co0.2Fe0.8S2. Effect of particle size on transition pressure could not be evaluated due to lack of available reports on bulk system.

  6. A new apparatus for the study of nuclear Bragg scattering

    SciTech Connect

    Siddons, D.P.; Hastings, J.B.; Faigel, G.

    1987-01-01

    A new monochromator system has been constructed which provides an energy resolution of 0.005 eV and an angular divergence of 0.4 arc seconds at an energy of 14.413 keV. In conjunction with a highly perfect crystal of isotopically enriched /sup 57/Fe/sub 2/O/sub 3/, a beam of nuclear resonant photons was extracted from the synchrotron continuum with signal to noise ratio of 100:1, and an intensity of >2 quanta/sec. 14 refs., 9 figs.

  7. Magnetic and Mössbauer studies of pure and Ti-doped YFeO 3 nanocrystalline particles prepared by mechanical milling and subsequent sintering

    NASA Astrophysics Data System (ADS)

    Khalifa, N. O.; Widatallah, H. M.; Gismelseed, A. M.; Al-Mabsali, F. N.; Sofin, R. G. S.; Pekala, M.

    2016-12-01

    Single-phased nanocrystalline particles of pure and 10 % Ti 4+-doped perovskite-related YFeO 3were prepared via mechanosynthesis at 450∘C. This temperature is ˜150-350 ∘C lower than those at which the materials, in bulk form, are normally prepared. Rietveld refinements of the X-ray diffraction patterns reveal that the dopant Ti 4+ ions prefer interstitial octahedral sites in the orthorhombic crystal lattice rather than those originally occupied by the expelled Fe 3+ ions. Magnetic measurements show canted antiferromagnetism in both types of nanoparticles. Doping with Ti 4+ lowers the Néel temperature of the YFeO 3 nanoparticles from ˜ 586 K to ˜ 521 K. The Ti 4+-doped YFeO 3 nanoparticles exhibit enhanced magnetization and coercivity but less magnetic hyperfine fields relative to the un-doped nanoparticles. The 57Fe Mössbauer spectra show ˜ 15 % of the YFeO 3 nanoparticles and ˜22 of Ti 4+-doped YFeO 3 ones to be superparamagnetic with blocking temperatures < 78 K. The broadened magnetic components in the 57Fe Mössbauer spectra suggest size-dependent hyperfine magnetic fields at the 57Fe nuclear sites and were associated with collective magnetic excitations. The 57Fe Mössbauer spectra show the local environments of the Fe 3+ ions in the superparamagnetic nanoparticles to be more sensitive to the presence of the Ti 4+ ions relative to those in the larger magnetic nanoparticles.

  8. In situ small-angle x-ray and nuclear resonant scattering study of the evolution of structural and magnetic properties of an Fe thin film on MgO (001)

    NASA Astrophysics Data System (ADS)

    Sharma, Gagan; Gupta, Ajay; Gupta, Mukul; Schlage, Kai; Wille, H.-C.

    2015-12-01

    Growth of magnetron sputtered Fe films on clean single crystalline MgO (001) substrate has been studied using in situ grazing incidence small angle x-ray scattering (GISAXS) and grazing incidence nuclear resonant scattering (GINRS) measurements. While GISAXS provides information about morphological changes, GINRS provides information about structural and magnetic properties, thus making it possible to correlate the evolution of magnetic properties with that of morphology and structure of the film. The film exhibits a Volmer-Weber type growth, with percolation transition occurring around 2 nm film thickness. Presence of a finite quadrupole splitting, as seen in GINRS measurements, suggests a significant distortion from cubic symmetry up to a film thickness of 3.5 nm, which can be attributed to hybridization between Fe 3 d and O 2 p orbitals at the interface as well as in-plane tensile strain induced as a result of coalescence of islands. Initially Fe islands exhibit superparamagnetic relaxation, while finite magnetic moment appears upon formation of macroscopic percolation islands. The film exhibits a weak perpendicular magnetic anisotropy (PMA), which vanishes concurrently with disappearance of structural distortion, suggesting that the observed PMA at least partly originates from inherent strain in the film. No presence of any known oxide of Fe was detected at the interface. More precise information about topological and magnetic structure of the interfaces between Fe and MgO layers is obtained using combined x-ray reflectivity and nuclear resonance reflectivity measurements on a 57Fe/MgO multilayer. Measurements show that about two monolayers of Fe at the interface have a reduced hyperfine field, providing evidence for hybridization with O atoms, as predicted by theory.

  9. Magnetic properties: M{umlt o}ssbauer, x-ray absorption spectroscopy, and specific-heat studies of Pr{sub 1.5}Ce{sub 0.5}{ital M}Sr{sub 2}Cu{sub 2}O{sub {ital z}} ({ital M}=Ta, In, Nb, Nb+Ga) compounds

    SciTech Connect

    Asaf, U.; Felner, I.; Schmitt, D.; Barbara, B.; Godart, C.; Alleno, E. |

    1996-12-01

    We have investigated Pr{sub 1.5}Ce{sub 0.5}{ital M}Sr{sub 2}Cu{sub 2}O{sub {ital z}} ({ital z}=9 or 10) materials ({ital M}=Ta, In, and Nb+Ga) by complementary experimental techniques. All materials studied are not superconducting. Magnetic susceptibility studies for {ital M}=Ta reveal one magnetic anomaly at 23 K and irreversibility phenomena at higher temperatures. The presence of 0.5{percent} {sup 57}Fe dramatically affects the positions of the anomalies, and M{umlt o}ssbauer spectroscopy studies (MS) reveal that the Cu(2) sites are magnetically ordered below {ital T}{sub {ital N}}(Cu)=130 K. This low {ital T}{sub {ital N}}(Cu) obtained is discussed. No specific heat anomaly was observed at 23 K, suggesting that the Pr sublattice does not order magnetically, and the anomalies in the susceptibility originate from the Cu moments. No anomalies in the susceptibility curves are found for {ital M}=In and Nb+Ga compounds. However, MS indicate that for the mixed compound, the Cu sites are magnetically ordered at low temperatures. The magnetic behavior of {ital M}=Ta is compared to similar systems with two anomalies for {ital M}=Nb at 11 and 52 K, and three anomalies for {ital M}=Ga at 12, 52, and 94 K. X-ray absorption spectroscopy (XAS) indicates that in all materials studied, the Pr has a mixed valence close to 3. The Pr valence does not change with temperature. {copyright} {ital 1996 The American Physical Society.}

  10. 5 7 Fe Mössbauer spectroscopic studies of single-crystalline K x Fe2- y S 2 and K x Fe2- y Se 2

    NASA Astrophysics Data System (ADS)

    Tsuchiya, Yuu; Ikeda, Shugo; Kobayashi, Hisao

    2016-12-01

    We have investigated the physical properties of single-crystalline K x Fe2- y S 2 and K x Fe2- y Se2 samples using 57Fe Mössbauer spectroscopy. The observed 57Fe Mössbauer spectra were reconstructed using a major antiferromagnetic ordered K2Fe4Se5 phase and a minor paramagnetic phase down to 5 K, despite being superconducting below 32.2 K in K x Fe2- y Se2. The analysis of 57Fe Mössbauer spectrum for K x Fe2- y S 2 at 290 K confirms the presence of a major antiferromagnetic ordered K2Fe4 S 5 phase and a minor paramagnetic phase in the K x Fe2- y S 2 single crystal. The derived hyperfine interaction parameters of the paramagnetic phase in K x Fe2- y S 2 suggest that the microstructure of this phase in K x Fe2- y S 2 is similar to that of the superconducting phase in K x Fe2- y Se2 although the K x Fe2- y S 2 single crystals exhibit no superconductivity down to 5 K.

  11. Nuclear Resonant Scattering Studies Under High Pressure and HighTtemperature

    NASA Astrophysics Data System (ADS)

    Sturhahn, W.; Lin, J.; Shen, G.; Jackson, J. M.; Zhao, J.; Prakapenka, V.; Lerche, M.; Bass, J. D.; Mao, H.

    2004-12-01

    Nuclear resonant scattering techniques have been applied very successfully to iron-bearing alloys [1-3] and silicates [4] under pressures in the Mbar regime using diamond anvil cells. The two main methods, nuclear resonant inelastic x-ray scattering (NRIXS) and synchrotron Mössbauer spectroscopy (SMS), will be discussed in their potential for the geophysical problem area. In general, NRIXS provides the phonon density of states [5] and sound velocities [6], whereas SMS gives access to the abundance of ferric iron and the spin state of iron in minerals and their polymorphs. % The introduction of Laser heating in combination with NRIXS and SMS at sector 3-ID of the Advanced Photon Source permits us now to conduct these studies under high pressure \\textit{and} high temperature. Here we will address two examples of this powerful, new opportunity. The reduction of sound velocities with increasing temperature, in particular for the shear wave, observed from NRIXS on hot, compressed iron metal in a pressure range of 40 GPa to 60 GPa. We find that the sound velocities do not depend on density alone but show an explicit temperature dependence. In a second experiment, we analyzed valence and spin state of iron in magnesium silicates. The starting material, orthoenstatite 57Fe0.1Mg0.9SiO3, was compressed in several steps up to 31 GPa in a diamond anvil cell. Each step involved laser annealing and the collection of SMS spectra at several temperatures. With x-ray diffraction we confirmed the creation of high-clinoenstatite, ringwoodite, ilmenite, and perovskite structures. Unique data on the iron behavior in each polymorph was obtained. % This work is supported by the U.S. DOE-BES, Office of Science, under Contract No. W-31-109-Eng-38 and by NSF through COMPRESS. % {}[1] H.K.Mao et al., Science \\textbf{292}, 914 (2001) [1mm] % {}[2] J.-F.Lin et al., Geophysical Research Letters \\textbf{30}, 2112 (2003) [1mm] % {}[3] W.L.Mao et al., Geophysical Research Letters \\textbf{31

  12. Thermodynamical Properties of 56Fe

    SciTech Connect

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

    2002-08-30

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

  13. Diffusion studies with synchrotron Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Jackson, J. M.

    2011-12-01

    Knowledge of diffusion properties is critical for understanding many physical and chemical processes in planetary interiors. For example, diffusion behavior provides constraints on chemical exchange and viscosity. Nuclear resonances open the window for observing diffusion properties under the extreme conditions that exist deep inside the Earth. Synchrotron Mössbauer spectroscopy (viz. nuclear forward scattering) makes use of synchrotron radiation coherently scattered in the forward direction after nuclear resonant excitation. The decay of the forward-scattered radiation is faster when atoms move on the time scale of the excited-state lifetime because of a loss of coherence. Such diffusion-activated processes lead to accelerated decay and line broadening in the measured signal. In the case of the Mössbauer active isotope 57Fe, the nuclear resonance at 14.4 keV has a natural lifetime of 141 ns. Therefore, one can observe diffusion events ranging from approximately one-sixth to 100 times the natural lifetime of 57Fe, which corresponds to diffusion coefficients of 10-16 and 10-13 m2/s, respectively and a two to three order of magnitude range of suitability. In this contribution, we will describe such measurements that access the microscopic details of the diffusion process for iron-bearing phases.

  14. Relevance of supramolecular interactions, texture and lattice occupancy in the designer iron(II) spin crossover complexes

    SciTech Connect

    Naik, Anil D.; Tinant, Bernard; Muffler, Kai; Wolny, Juliusz A.; Schuenemann, Volker; Garcia, Yann

    2009-06-15

    New Fe{sup II} complexes of formula [Fe(3-Br-phen){sub 2}(NCS){sub 2}].Solvent (Solvent=0.5 CH{sub 3}OH (1), 2 CH{sub 2}Cl{sub 2} (2), desolvation of 2 (3), 0.5 CH{sub 3}COCH{sub 3} (4) and 0 (5)) have been synthesized. {sup 57}Fe Moessbauer and magnetic investigation reveal unique features atypical of classic [Fe(phen){sub 2}(NCS){sub 2}] polymorphs. Complex 1, prepared by precipitation in MeOH, undergoes upon cooling below room temperature an incomplete and gradual thermally induced spin conversion, while 4 prepared by an extraction method remains mostly in the low-spin state. The non solvated compounds 3 and 5, display a more abrupt spin crossover on cooling around T{sub 1/2}=175 K and T{sub 1/2}=198 K, respectively. Defects/soft lattice inclusion due to different methods of material synthesis, extent of aging, reaction medium and associated solvent molecules have enormous influence on the particle size and magnetic properties of these complexes. Scanning electron micrographs helps to establish a logical relationship among methods employed for synthesis, texture of materials and their effect on magnetic properties. The crystal structure of 2 determined in the monoclinic space group P2/c (100 K) reveals a mononuclear complex consisting of a distorted FeN{sub 6} octahedron in the low-spin state, constructed from two 3-bromo-1, 10-phenanthroline and two isothiocyanato anions in cis position. Intermolecular interactions between mononuclear units of the S...Br, S...C(H) and pi-pi type afford a 2D supramolecular network. DFT calculations for the single molecule 2 reveals an energy difference between high-spin and low-spin isomers of 7 kJ/mol suggesting a slight destabilization of the low-spin state compared to [Fe(phen){sub 2}(NCS){sub 2}]. Normal co-ordinate analysis was also carried out for 3 and compared with experimental temperature dependent Raman spectra for 5. - Graphical abstract: New Fe{sup II} complexes of formula [Fe(3-Br-phen){sub 2}(NCS){sub 2}].Solvent

  15. Iron oxide nanoparticles for plant nutrition? A preliminary Mössbauer study

    NASA Astrophysics Data System (ADS)

    Homonnay, Z.; Tolnai, Gy.; Fodor, F.; Solti, Á.; Kovács, K.; Kuzmann, E.; Ábrahám, A.; Szabó, E. Gy.; Németh, P.; Szabó, L.; Klencsár, Z.

    2016-12-01

    One of the most important micronutrients for plants is iron. We have prepared iron(III) oxyhydroxide and magnetite nanoparticles with the aim to use them as possible nutrition source for plants. The iron(III)-oxide/oxyhydroxide nanoparticles prepared under our experimental conditions as colloidal suspensions proved to be 6-line ferrihydrite nanoparticles as verified by XRD, TEM/SAED and Mössbauer spectroscopy measurements. 57Fe Mössbauer spectra of magnetite nanoparticles prepared under different preparation conditions could be analyzed on the basis of a common model based on the superposition of four sextet components displaying Gaussian-shaped hyperfine magnetic field distributions.

  16. Structural and Mossbauer Studies of Fe Doped ZnO Nanocrystals

    NASA Astrophysics Data System (ADS)

    Dhiman, Pooja; Kumar, S.; Gautam, Ashish; Singh, M.

    2011-12-01

    Zn1-xFexO (x = 0.01, 0.02, 0.03, 0.04, 0.1) nanoparticles synthesized by a solution combustion method were characterized by different techniques. The structural characterization by XRD confirmed the phase purity of the samples. The optical characterization of the nanoparticles by FTIR revealed the formation of wurtzite structure. Local environment around Fe atoms has been probed by 57Fe Mossbauer spectroscopy and measured isomer shifts confirmed the charge state of iron is Fe3+.

  17. Mössbauer and XRD study of intercalated CaFe-layered double hydroxides

    NASA Astrophysics Data System (ADS)

    Sipiczki, Mónika; Kuzmann, Ernő; Pálinkó, István; Homonnay, Zoltán; Sipos, Pál; Kukovecz, Ákos; Kónya, Zoltán

    2014-04-01

    N-containing fully saturated (L-prolinate) or aromatic (indole-2-carboxylate) heterocyclic anions were immobilised in CaFe-layered double hydroxide with the dehydration-rehydration method from aqueous ethanol or acetone. The structure of the resulting organic-inorganic hybrids was characterised mainly with powder X-ray diffraction and 57Fe Mössbauer spectroscopy, and as supplementary analysis scanning electron microscopy, energy dispersive X-ray spectroscopy with elemental mapping and molecular modelling were also applied. It was found that the solvent mixture used for the synthesis caused enormous difference in the interlayer spacings of the obtained inorganic-organic hybrids.

  18. A study of defects in iron-based binary alloys by the Mössbauer and positron annihilation spectroscopies

    SciTech Connect

    Idczak, R. Konieczny, R.; Chojcan, J.

    2014-03-14

    The room temperature positron annihilation lifetime spectra and {sup 57}Fe Mössbauer spectra were measured for pure Fe as well as for iron-based Fe{sub 1−x}Re{sub x}, Fe{sub 1−x}Os{sub x}, Fe{sub 1−x}Mo{sub x}, and Fe{sub 1−x}Cr{sub x} solid solutions, where x is in the range between 0.01 and 0.05. The measurements were performed in order to check if the known from the literature, theoretical calculations on the interactions between vacancies and solute atoms in iron can be supported by the experimental data. The vacancies were created during formation and further mechanical processing of the iron systems under consideration so the spectra mentioned above were collected at least twice for each studied sample synthesized in an arc furnace— after cold rolling to the thickness of about 40 μm as well as after subsequent annealing at 1270 K for 2 h. It was found that only in Fe and the Fe-Cr system the isolated vacancies thermally generated at high temperatures are not observed at the room temperature and cold rolling of the materials leads to creation of another type of vacancies which were associated with edge dislocations. In the case of other cold-rolled systems, positrons detect vacancies of two types mentioned above and Mössbauer nuclei “see” the vacancies mainly in the vicinity of non-iron atoms. This speaks in favour of the suggestion that in iron matrix the solute atoms of Os, Re, and Mo interact attractively with vacancies as it is predicted by theoretical computations and the energy of the interaction is large enough for existing the pairs vacancy-solute atom at the room temperature. On the other hand, the corresponding interaction for Cr atoms is either repulsive or attractive but smaller than that for Os, Re, and Mo atoms. The latter is in agreement with the theoretical calculations.

  19. Thermal low spin-high spin equilibrium of Fe(II) in thiospinels CuFe{sub 0.5}(Sn{sub (1-x)}Ti{sub x}){sub 1.5}S{sub 4} (0{<=}x{<=}1)

    SciTech Connect

    Womes, M.; Reibel, C.; Mari, A.; Zitoun, D.

    2011-04-15

    A series of spinel compounds with composition CuFe{sub 0.5}(Sn{sub (1-x)}Ti{sub x}){sub 1.5}S{sub 4} (0{<=}x{<=}1) is analysed by X-ray diffraction, measurements of magnetic susceptibilities and {sup 57}Fe Moessbauer spectroscopy. All samples show a temperature-dependent equilibrium between an electronic low spin 3d(t{sub 2g}){sup 6}(e{sub g}){sup 0} and a high spin 3d(t{sub 2g}){sup 4}(e{sub g}){sup 2} state of the Fe(II) ions. The spin crossover is of the continuous type and extends over several hundred degrees in all samples. The Sn/Ti ratio influences the thermal equilibrium between the two spin states. Substitution of Sn(IV) by the smaller Ti(IV) ions leads to a more compact crystal lattice, which, in contrast to many metal-organic Fe(II) complexes, does not stabilise the low spin state, but increases the residual high spin fraction for T{yields}0 K. The role played by antiferromagnetic spin coupling in the stabilisation of the high spin state is discussed. The results are compared with model calculations treating the effect of magnetic interactions on spin state equilibria. -- Graphical Abstract: Comparison of fractions of high spin Fe(II) from Moessbauer spectra (circles) with plots of {chi}{sub m}T (dots) versus T. Discrepancies between both methods indicate anti-ferromagnetic spin coupling. Display Omitted Research highlights: {yields} Many Fe(II) complexes show thermally induced high spin-low spin crossover. {yields} Spin crossover in spinel compounds is extremely scarce. {yields} Usually, lattice contraction favours the low spin state in Fe(II) complexes. {yields} In these spinels, lattice contraction favours the high spin state. {yields} The stabilisation of the high spin state is explained by spin-spin interactions.

  20. Application of Mössbauer spectroscopy in magnetism

    NASA Astrophysics Data System (ADS)

    Keune, Werner

    2012-03-01

    An overview is provided on our recent work that applies 57Fe Mössbauer spectroscopy to specific problems in nanomagnetism. 57Fe conversion electron Mössbauer spectroscopy (CEMS) in conjunction with the 57Fe probe layer technique as well as 57Fe nuclear resonant scattering (NRS) were employed for the study of various nanoscale layered systems: (i) metastable fct-Fe; a strongly enhanced hyperfine magnetic field Bhf of ˜39 T at 25 K was observed in ultrahigh vacuum (UHV) on uncoated three-monolayers thick epitaxial face-centered tetragonal (fct) 57Fe(110) ultrathin films grown by molecular-beam epitaxy (MBE) on vicinal Pd(110) substrates; this indicates the presence of enhanced Fe local moments, μFe, as predicted theoretically; (ii) Fe spin structure; by applying magnetic fields, the Fe spin structure during magnetization reversal in layered (Sm-Co)/Fe exchange spring magnets and in exchange-biased Fe/MnF2 bilayers was proven to be non-collinear and depth-dependent; (iii) ferromagnet/semiconductor interfaces for electrical spin injection; CEMS was used as a diagnostic tool for the investigation of magnetism at the buried interface of Fe electrical contacts on the clean surface of GaAs(001) and GaAs(001)-based spin light-emitting diodes (spin LED) with in-plane or out-of-plane Fe spin orientation; the measured rather large average hyperfine field of ˜27 T at 295 K and the distribution of hyperfine magnetic fields, P(Bhf), provide evidence for the absence of magnetically "dead" layers and the existence of relatively large Fe moments (μFe ˜ 1.8 μB) at the ferromagnet/semiconductor interface. - Finally, a short outlook is given for potential applications of Mössbauer spectroscopy on topical subjects of nanomagnetism/spintronics.

  1. Structural and magnetic study of Al{sup 3+} doped Ni{sub 0.75}Zn{sub 0.25}Fe{sub 2−x}Al{sub x}O{sub 4} nanoferrites

    SciTech Connect

    Wang, L.; Rai, B.K.; Mishra, S.R.

    2015-05-15

    Graphical abstract: Hyperfine field of individual sites (inset) and weighted average hyperfine field as a function of Al{sup 3+} content for Ni{sub 0.75}Zn{sub 0.25}Fe{sub 2−x}Al{sub x}O{sub 4}. - Highlights: • Grain size reduction with Al{sup 3+} substitution. • Preferred occupancy of Al{sup 3+} at B site for higher Al{sup 3+} content. • Reduction in Ms, Tc, and hyperfine field with increasing Al{sup 3+} content. • Size dependent variation in coercivity. • Changes in isomer shift due to competing effect of volume and substitution. - Abstract: Nanostructured Al{sup 3+} doped Ni{sub 0.75}Zn{sub 0.25}Fe{sub 2−x}Al{sub x}O{sub 4} (x = 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0) ferrites were synthesized via the wet chemical method. X-ray diffraction, transmission electron microscopy, and magnetization measurements have been used to investigate the structural and magnetic properties of spinel ferrites calcined at 950 °C. With the doping of Al{sup 3+}, the particle size of Ni{sub 0.75}Zn{sub 0.25}Fe{sub 2−x}Al{sub x}O{sub 4} first increased to 47 nm at x = 0.4 and then decreased down to 37 nm at x = 1. The main two absorption bands in IR spectra were observed around 600 cm{sup −1} and 400 cm{sup −1} corresponding to stretching vibration of tetrahedral and octahedral group Fe{sup 3+}–O{sup 2−}. Saturation magnetization and hyperfine field values decreased linearly with Al{sup 3+} due to magnetic dilution and the relative strengths of Fe–O–Me (Me = Fe, Ni, Zn, and Al) superexchanges. The coercive field showed an inverse dependence on ferrite particle size with minimum value of 82 Oe for x = 0.4. A continuous drop in Curie temperature was observed with the Al{sup 3+} substitution. From the Moessbauer spectral analysis and X-ray diffraction analysis, it is deduced that Al{sup 3+} for x < 0.4 has no obvious preference for either tetrahedral or octahedral site but has a greater preference for the B site for x > 0.4. In nutshell the study presents detailed

  2. Unraveling the electronic structures of low-valent naphthalene and anthracene iron complexes: X-ray, spectroscopic, and density functional theory studies.

    PubMed

    Schnöckelborg, Eva-Maria; Khusniyarov, Marat M; de Bruin, Bas; Hartl, František; Langer, Thorsten; Eul, Matthias; Schulz, Stephen; Pöttgen, Rainer; Wolf, Robert

    2012-06-18

    Naphthalene and anthracene transition metalates are potent reagents, but their electronic structures have remained poorly explored. A study of four Cp*-substituted iron complexes (Cp* = pentamethylcyclopentadienyl) now gives rare insight into the bonding features of such species. The highly oxygen- and water-sensitive compounds [K(18-crown-6){Cp*Fe(η(4)-C(10)H(8))}] (K1), [K(18-crown-6){Cp*Fe(η(4)-C(14)H(10))}] (K2), [Cp*Fe(η(4)-C(10)H(8))] (1), and [Cp*Fe(η(4)-C(14)H(10))] (2) were synthesized and characterized by NMR, UV-vis, and (57)Fe Mössbauer spectroscopy. The paramagnetic complexes 1 and 2 were additionally characterized by electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility measurements. The molecular structures of complexes K1, K2, and 2 were determined by single-crystal X-ray crystallography. Cyclic voltammetry of 1 and 2 and spectroelectrochemical experiments revealed the redox properties of these complexes, which are reversibly reduced to the monoanions [Cp*Fe(η(4)-C(10)H(8))](-) (1(-)) and [Cp*Fe(η(4)-C(14)H(10))](-) (2(-)) and reversibly oxidized to the cations [Cp*Fe(η(6)-C(10)H(8))](+) (1(+)) and [Cp*Fe(η(6)-C(14)H(10))](+) (2(+)). Reduced orbital charges and spin densities of the naphthalene complexes 1(-/0/+) and the anthracene derivatives 2(-/0/+) were obtained by density functional theory (DFT) methods. Analysis of these data suggests that the electronic structures of the anions 1(-) and 2(-) are best represented by low-spin Fe(II) ions coordinated by anionic Cp* and dianionic naphthalene and anthracene ligands. The electronic structures of the neutral complexes 1 and 2 may be described by a superposition of two resonance configurations which, on the one hand, involve a low-spin Fe(I) ion coordinated by the neutral naphthalene or anthracene ligand L, and, on the other hand, a low-spin Fe(II) ion coordinated to a ligand radical L(•-). Our study thus reveals the redox noninnocent character of the naphthalene

  3. Iron isotope fractionation between pyrite (FeS 2), hematite (Fe 2O 3) and siderite (FeCO 3): A first-principles density functional theory study

    NASA Astrophysics Data System (ADS)

    Blanchard, Marc; Poitrasson, Franck; Méheut, Merlin; Lazzeri, Michele; Mauri, Francesco; Balan, Etienne

    2009-11-01

    In addition to equilibrium isotopic fractionation factors experimentally derived, theoretical predictions are needed for interpreting isotopic compositions measured on natural samples because they allow exploring more easily a broader range of temperature and composition. For iron isotopes, only aqueous species were studied by first-principles methods and the combination of these data with those obtained by different methods for minerals leads to discrepancies between theoretical and experimental isotopic fractionation factors. In this paper, equilibrium iron isotope fractionation factors for the common minerals pyrite, hematite, and siderite were determined as a function of temperature, using first-principles methods based on the density functional theory (DFT). In these minerals belonging to the sulfide, oxide and carbonate class, iron is present under two different oxidation states and is involved in contrasted types of interatomic bonds. Equilibrium fractionation factors calculated between hematite and siderite compare well with the one estimated from experimental data (ln α57Fe/ 54Fe = 4.59 ± 0.30‰ and 5.46 ± 0.63‰ at 20 °C for theoretical and experimental data, respectively) while those for Fe(III) aq-hematite and Fe(II) aq-siderite are significantly higher that experimental values. This suggests that the absolute values of the reduced partition functions ( β-factors) of aqueous species are not accurate enough to be combined with those calculated for minerals. When compared to previous predictions derived from Mössbauer or INRXS data [Polyakov V. B., Clayton R. N., Horita J. and Mineev S. D. (2007) Equilibrium iron isotope fractionation factors of minerals: reevaluation from the data of nuclear inelastic resonant X-ray scattering and Mössbauer spectroscopy. Geochim. Cosmochim. Acta71, 3833-3846], our iron β-factors are in good agreement for siderite and hematite while a discrepancy is observed for pyrite. However, the detailed investigation of the

  4. Iron isotope fractionation in sulfides: constraints on mechanisms of sulfide formations in hydrothermal and magmatic systems.

    NASA Astrophysics Data System (ADS)

    Polyakov, Veniamin; Soultanov, Dilshod

    2010-05-01

    deposit of Crasberg igneous complex (GIC) [8]. In this case, pyrite is enriched in heavy iron isotope relative to chalcopyrite that is in agreement with direction of iron isotope fractionation in equilibrium. Using these data [8] and appropriate iron β-factors obtained from INRXS- and Moessbauer experiments, we estimated temperatures of pyrite and chalcopyrite formation. We obtained reasonable temperatures varying between 180 and 650oC for different intrusions of GIC, which are in agreement with other estimations [9,10] Conclusions: Iron β-factors for chalcopyrite CuFeS2 were calculated from 57Fe PDOS obtained in INRXS synchrotron radiation experiments [1]. Iron β-factors for mackinawite were calculated from the Moessbauer SOD shift based on experiments [4]. Using new value of chalcopyrite and mackinawite and/or troilite iron β-factors, it was shown that isotope composition of pyrite in hydrothermal seafloor processes is controlled by equilibrium isotope fractionation between FeS phase (pyrite precursor) and hydrothermal fluid. Fe isotope equilibrium between pyrite and chalcopyrite may be attained in magmatic processes. References: Kobayashi H., Umemura J., Kazekami Y. and Sakai N. Phys. Rev. B. (2007) 76, 134108. Polyakov V. B., Mineev S. D., Clayton R. N., Hu G. and Mineev K. S. Geochim. Cosmochim. Acta (2005) 69, 5531-5536. Polyakov V. B., Clayton R. N., Horita J. and Mineev S.D. Geochim. Cosmochim. Acta (2007) 71, 3833-3846. Bertaut E. F., Burlet P. and Chappert J. Solid State Comm. (1965) 3, 335 - 338. Polyakov V. B. Geochim. Cosmochim. Acta (1997)61, 4213 - 4217. Polyakov V.B. and Mineev S. D. Geochim. Cosmochim. Acta (2000) 64, 849 - 865 Rouxel O., Shanks III W. C., Bach W. and Edwards K. J. Chem. Geol. (2008) 252, 214 - 227 Graham S., Pearson N., Jackson S., Griffin W. and O'Reilly S. Y. Chem. Geol. (2004) 204, 147 - 169 Heinrich C. A. Mineralium Deposita (2005) 39, 864-889 Pollard P.J. and Taylor R.G. Mineralium Deposita (2004) 37, 117-136. .

  5. Mono- and Dinuclear Iron Complexes of Bis(1-methylimidazol-2-yl)ketone (bik): Structure, Magnetic Properties and Catalytic Oxidation Studies

    PubMed Central

    Bruijnincx, Pieter C. A.; Buurmans, Inge L. C.; Huang, Yuxing; Juhász, Gergely; Viciano-Chumillas, Marta; Quesada, Manuel; Reedijk, Jan; Lutz, Martin; Spek, Anthony L.; Münck, Eckard; Bominaar, Emile L.; Klein Gebbink, Robertus J. M.

    2011-01-01

    The newly synthesized dinuclear complex [FeIII2(μ-OH)2(bik)4](NO3)4 (1) (bik, bis(1-methylimidazol-2-yl)ketone) shows rather short Fe···Fe (3.0723(6) Å) and Fe–O distances (1.941(2)/1.949(2) Å) compared to other unsupported FeIII2(μ-OH)2 complexes. The bridging hydroxide groups of 1 are strongly hydrogen bonded to a nitrate anion. The 57Fe isomer shift (δ = 0.45 mm s−1) and quadrupole splitting (ΔEQ = 0.26 mm s−1) obtained from Mössbauer spectroscopy are consistent with the presence of two identical high-spin iron(III) sites. Variable temperature magnetic susceptibility studies revealed antiferromagnetic exchange (J = 35.9 cm−1 and = JS1·S2) of the metal ions. The optimized DFT geometry of the cation of 1 in the gas phase agrees well with the crystal structure, but both the Fe···Fe and Fe-OH distances are overestimated (3.281 and 2.034 Å, respectively). The agreement in these parameters improves dramatically (3.074 and 1.966 Å) when the hydrogen-bonded nitrate groups are included, reducing the value calculated for J by 35%. Spontaneous reduction of 1 was observed in methanol, yielding a blue [FeII(bik)3]2+ species. Variable temperature magnetic susceptibility measurements of [FeII(bik)3](OTf)2 (2) revealed spin crossover behavior. Thermal hysteresis was observed with 2, due to a loss of co-crystallized solvent molecules, as monitored by thermogravimetric analysis. The hysteresis disappears once the solvent is fully depleted by thermal cycling. [FeII(bik)3](OTf)2 (2) catalyzes the oxidation of alkanes with t-BuOOH. High selectivity for tertiary C-H bond oxidation was observed with adamantane (3°/2° value of 29.6); low alcohol/ketone ratios in cyclohexane and ethylbenzene oxidation, a strong dependence of total turnover number on the presence of O2, and a low retention of configuration in cis-1,2-dimethylcyclohexane oxidation were observed. Stereoselective oxidation of olefins with dihydrogen peroxide yielding epoxides was observed under

  6. Mono- and dinuclear iron complexes of bis(1-methylimidazol-2-yl)ketone (bik): structure, magnetic properties, and catalytic oxidation studies.

    PubMed

    Bruijnincx, Pieter C A; Buurmans, Inge L C; Huang, Yuxing; Juhász, Gergely; Viciano-Chumillas, Marta; Quesada, Manuel; Reedijk, Jan; Lutz, Martin; Spek, Anthony L; Münck, Eckard; Bominaar, Emile L; Klein Gebbink, Robertus J M

    2011-10-03

    The newly synthesized dinuclear complex [Fe(III)(2)(μ-OH)(2)(bik)(4)](NO(3))(4) (1) (bik, bis(1-methylimidazol-2-yl)ketone) shows rather short Fe···Fe (3.0723(6) Å) and Fe-O distances (1.941(2)/1.949(2) Å) compared to other unsupported Fe(III)(2)(μ-OH)(2) complexes. The bridging hydroxide groups of 1 are strongly hydrogen-bonded to a nitrate anion. The (57)Fe isomer shift (δ = 0.45 mm s(-1)) and quadrupole splitting (ΔE(Q) = 0.26 mm s(-1)) obtained from Mössbauer spectroscopy are consistent with the presence of two identical high-spin iron(III) sites. Variable-temperature magnetic susceptibility studies revealed antiferromagnetic exchange (J = 35.9 cm(-1) and H = JS(1)·S(2)) of the metal ions. The optimized DFT geometry of the cation of 1 in the gas phase agrees well with the crystal structure, but both the Fe···Fe and Fe-OH distances are overestimated (3.281 and 2.034 Å, respectively). The agreement in these parameters improves dramatically (3.074 and 1.966 Å) when the hydrogen-bonded nitrate groups are included, reducing the value calculated for J by 35%. Spontaneous reduction of 1 was observed in methanol, yielding a blue [Fe(II)(bik)(3)](2+) species. Variable-temperature magnetic susceptibility measurements of [Fe(II)(bik)(3)](OTf)(2) (2) revealed spin-crossover behavior. Thermal hysteresis was observed with 2, due to a loss of cocrystallized solvent molecules, as monitored by thermogravimetric analysis. The hysteresis disappears once the solvent is fully depleted by thermal cycling. [Fe(II)(bik)(3)](OTf)(2) (2) catalyzes the oxidation of alkanes with t-BuOOH. High selectivity for tertiary C-H bond oxidation was observed with adamantane (3°/2° value of 29.6); low alcohol/ketone ratios in cyclohexane and ethylbenzene oxidation, a strong dependence of total turnover number on the presence of O(2), and a low retention of configuration in cis-1,2-dimethylcyclohexane oxidation were observed. Stereoselective oxidation of olefins with dihydrogen

  7. Circulating non–transferrin-bound iron after oral administration of supplemental and fortification doses of iron to healthy women: a randomized study1234

    PubMed Central

    Andersson, Maria; Egli, Ines; Foman, Jasmin Tajeri; Zeder, Christophe; Westerman, Mark E; Hurrell, Richard F

    2014-01-01

    Background: After the oral administration of iron, the production of circulating non–transferrin-bound iron may contribute to an increased risk of illness in malaria-endemic areas that lack effective medical services. Objective: In healthy women with a range of body iron stores, we aimed to determine effects on the production of circulating non–transferrin-bound iron resulting from the oral administration of 1) a supplemental dose of iron (60 mg) with water, 2) a supplemental dose of iron (60 mg) with a standard test meal, and 3) a fortification dose of iron (6 mg) with a standard test meal. Design: With the use of serum ferritin as the indicator, healthy women with replete iron stores (ferritin concentration >25 μg/L; n = 16) and reduced iron stores (ferritin concentration ≤25 μg/L; n = 16) were enrolled in a prospective, randomized, crossover study. After the oral administration of aqueous solutions of ferrous sulfate isotopically labeled with 54Fe, 57Fe, or 58Fe, blood samples were collected for 8 h, and iron absorption was estimated by erythrocyte incorporation at 14 d. Results: At 4 h, serum non–transferrin-bound iron reached peaks with geometric mean (95% CI) concentrations of 0.81 μmol/L (0.56, 1.1 μmol/L) for 60 mg Fe with water and 0.26 μmol/L (0.15, 0.38 μmol/L) for 60 mg Fe with food but was at assay limits of detection (0.1 μmol Fe/L) for 6 mg Fe with food. For the 60 mg Fe without food, the area under the curve over 8 h for serum non–transferrin-bound iron was positively correlated with the amount of iron absorbed (R = 0.49, P < 0.01) and negatively correlated with serum ferritin (R = −0.39, P < 0.05). Conclusions: In healthy women, the production of circulating non–transferrin-bound iron is determined by the rate and amount of iron absorbed. The highest concentrations of non–transferrin-bound iron resulted from the administration of supplemental doses of iron without food. Little or no circulating non–transferrin-bound iron

  8. Study on spin configuration in photoresponsive iron mixed-valence complexes by Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Okazawa, A.; Yoshida, J.; Kida, N.; Kashima, I.; Murata, W.; Enomoto, M.; Kojima, N.

    2014-04-01

    We have investigated magnetic properties in a series of photoresponsive dithiooxalato (dto)-bridged iron mixed-valence complexes, (SP-R)[FeIIFeIII(dto)3] (SP-R = R-substituted pyridospiropyran cation; R = Me, Et, and Pr; abbreviated as 1 Me, 1 Et, and 1 Pr, respectively). As for our previous reports, 1 Me and 1 Et show two-step succeeding ferromagnetic transitions at T C = 25 & 8 K and 22 & 5 K, respectively. However, 1 Et has no hysteresis in the magnetic susceptibility, while 1 Me undergoes the charge transfer phase transition with thermal hysteresis around 75 K. To elucidate the two-step transitions of them, we measured 57Fe Mössbauer spectra of 1 Et. The spectra of FeII ( S = 2) and FeIII ( S = 1/2) in the HTP were observed in the magnetically ordered state as well as the paramagnetic state, and revealed that only HTP exists in a temperature range up to 5 K. The result is consistent with that of 1 Pr, where one ferromagnetic phase transition occurs at T C = 10 K. 57Fe Mössbauer spectroscopy is useful to clarify the origin of the succeeding magnetic transition for these systems.

  9. Etudes structurales de composés de type cémentite: Effet de l'hydroge`ne sur Fe 3C suivi par diffraction neutronique. Spectrométrie Mössbauer sur FeCo 2B et Co 3B dopés au 57Fe

    NASA Astrophysics Data System (ADS)

    Fruchart, D.; Chaudouet, P.; Fruchart, R.; Rouault, A.; Senateur, J. P.

    1984-02-01

    Accurate neutron diffractograms obtained using Fe 3C powdered samples have been recorded using position sensitive detectors. The structure parameters have been determined in the 20-650°C range both in vacuo and in hydrogen atmosphere. No significant location of hydrogen atoms in the cell could be detected before the complete decomposition of Fe 3C, which is considerably enhanced by H 2 gas and is accompanied by an initial loss of carbon (<5%). The magnetic diffraction peaks correspond to ferromagnetic moments directed along the yaxis: M(4 c) ⋍ M(8f) = 1.8 ± 0.1 μ B(extrapolated). Such a value agrees reasonably well with those obtained from Mössbauer data. Comparison with the isomorphous borides or Fe-substitutedCo 3X compounds indicates that a rigid band model is inadequate to describe the electronic scheme of Fe in cementite and related compounds. Analysis of the stability of M3Xcementite-type structured materials reveals the major role of M(d)-X(p) hybridization.

  10. Decay of {sup 161m1,m2}Dy isomers under conditions of a resonance environment (Moessbauer Screen)

    SciTech Connect

    Loginov, Yu. E. Zinoviev, V. G.; Kabina, L. P.; Lisin, S. S.; Maljutenkov, Ed. I.

    2013-06-15

    The half-lives of the isomers {sup 161m1}Dy and {sup 161m2}Dy (E = 25.6 keV and T{sub 1/2} {approx} 30 ns for the former and E = 74.6 keV and T{sub 1/2} {approx} 3 ns for the latter) placed in a {sup 160}Gd{sub 2}O{sub 3} crystal lattice at T = 300 K and surrounded by stable {sup 161}Dy nuclei in the composition of {sup 161}Dy{sub 2}O{sub 3} were measured by the method of ({beta}-{gamma}) coincidences in the beta-decay process {sup 161}Tb {yields} {sup 161}Dy. Nuclei of {sup 161m1,m2}Dy were obtained according to the chain {sup 160}Gd(n, {gamma}){sup 161}Gd {yields} {sup 161}Tb {yields} {sup 161}Dy from {sup 160}Dy{sub 2}O{sub 3} weighted portions irradiated at the PWR-M reactor of the Petersburg Nuclear Physics Institute (PNPI, Gatchina, Russia). The T{sub 1/2} value observed for the isomer {sup 161m1}Dy was found to be correlated with the number of surrounding {sup 161}Dy nuclei. The presence of this correlation in {sup 161m1}Dy can be explained by the multiple resonance scattering of photons from isomer decay within the sample used. No such correlation was observed for {sup 161m2}Dy. The half-lives measured for the isomers {sup 161m1}Dy and {sup 161m2}Dy in the absence of the above environment are 29.2(1) and 3.50(1) ns, respectively.

  11. Moessbauer/XRF MIMOS Instrumentation and Operation During the 2012 Analog Field Test on Mauna Kea Volcano, Hawaii

    NASA Technical Reports Server (NTRS)

    Graff, Trevor G.; Morris, R. V.; Klingelhofer, G.; Blumers, M.

    2013-01-01

    Field testing and scientific investigations were conducted on the Mauna Kea Volcano, Hawaii, as part of the 2012 Moon and Mars Analog Mission Activities (MMAMA). Measurements were conducted using both stand-alone and rover-mounted instruments to determine the geophysical and geochemical properties of the field site, as well as provide operational constraints and science considerations for future robotic and human missions [1]. Reported here are the results from the two MIMOS instruments deployed as part of this planetary analog field test.

  12. Pressure dependence of the electronic and magnetic properties of the layered antiferromagnetic insultaor FeI[sub 2

    SciTech Connect

    Hearne, G.R.; Sterer, E.; Pasternak, M.P. ); Taylor, R.D. )

    1994-07-10

    Nuclear hyperfine interaction parameters have been deduced from [sup 57]Fe Moessbauer spectra recorded in the range of 0--26 GPa and at temperatures of 10--296 K in anhydrous ferrous iodide. X-ray diffraction data indicate that the compound is isostructral in the range 0--25 GPa. There is an abrupt change in the electronic state and spin dynamics of the transition-metal ([ital TM]) atom, and in the magnetic behavior of the compound at 20 GPa. In the range 0--19 GPa, antiferromagnetic ordering occurs below well-defined Neel temperatures T[sub N]. T[sub N] increases by more than ten-fold and static internal fields of up to 12 Tesla are generated at the [ital TM] nuclear site. At pressures higher than 20 GPa hyperfine structure associated with atomic-spin fluctuations are evident down to 10 K. An enhanced dynamic internal field of [similar to]30 Tesla --- associated with the spin fluctuations --- is sensed by the iron nucleus. No static magnetic ordering due to cooperative exchange interactions is observed above 20 GPa, in contrast to the magnetism that occurs in the low pressure regime. [copyright]American Institute of Phyiscs

  13. Extracellular iron-sulfur precipitates from growth of Desulfovibrio desulfuricans

    SciTech Connect

    Antonio, M. R.; Tischler, M. L.; Witzcak, D.

    1999-12-20

    The authors have examined extracellular iron-bearing precipitates resulting from the growth of Desulfovibrio desulfuricans in a basal medium with lactate as the carbon source and ferrous sulfate. Black precipitates were obtained when D. desulfuricans was grown with an excess of FeSO{sub 4}. When D. desulfuricans was grown under conditions with low amounts of FeSO{sub 4}, brown precipitates were obtained. The precipitates were characterized by iron K-edge XAFS (X-ray absorption fine structure), {sup 57}Fe Moessbauer-effect spectroscopy, and powder X-ray diffraction. Both were noncrystalline and nonmagnetic (at room temperature) solids containing high-spin Fe(III). The spectroscopic data for the black precipitates indicate the formation of an iron-sulfur phase with 6 nearest S neighbors about Fe at an average distance of 2.24(1) {angstrom}, whereas the brown precipitates are an iron-oxygen-sulfur phase with 6 nearest O neighbors about Fe at an average distance of 1.95(1) {angstrom}.

  14. Magnetic properties of cobalt-ferrite nanoparticles embedded in polystyrene resin

    SciTech Connect

    Vaishnava, P. P.; Senaratne, U.; Buc, E.; Naik, R.; Naik, V. M.; Tsoi, G.; Wenger, L. E.; Boolchand, P.

    2006-04-15

    Samples of maghemite and cobalt-ferrite nanoparticles (sizes, 3-10 nm) were prepared by cross-linking sulfonated polystyrene resin with aqueous solutions of (1) FeCl{sub 2}, (2) 80%FeCl{sub 2}+20%CoCl{sub 2}, (3) FeCl{sub 3}, and (4) 80%FeCl{sub 3}+20%CoCl{sub 2} by volume. Chemical analysis, x-ray powder-diffraction, and {sup 57}Fe Moessbauer spectroscopic measurements show that samples 1 and 3 consist of {gamma}-Fe{sub 2}O{sub 3} nanoparticles (sizes, {approx}10 and 3 nm) and sample 2 and 4 consist of Co{sub x}Fe{sub 3-x}O{sub 4} nanoparticles (sizes, {approx}10 and 4 nm). The temperature dependence of the zero-field-cooled and field-cooled magnetizations at low temperatures, together with a magnetic hysteresis in the M versus H data below blocking temperatures, demonstrate superparamagnetic behavior. The introduction of Co in the iron oxide-resin matrix results in an increase in the blocking temperature of nanoparticles.

  15. Structure and magnetic properties of Y{sub 1-x}Lu{sub x}FeO{sub 3} (0 {<=} x {<=} 1) ceramics

    SciTech Connect

    Yuan Xueping; Tang Yankun; Sun Yue; Xu Mingxiang

    2012-03-01

    Polycrystalline Lu-doped YFeO{sub 3} samples with perovskite structure were synthesized by solid-state reaction. Powder X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray analysis manifest the high quality of the samples. Room temperature {sup 57}Fe Moessbauer spectra indicate that only the Fe{sup 3+} exists in the samples, which excludes the formation of multiple valence of Fe. The large effective magnetic moments of Fe{sup 3+} obtained from the temperature dependence of magnetization data can be explained in terms of the formation of ferromagnetic clusters. Field-dependent magnetization reveals that all the samples show weak ferromagnetic property due to the small canting of the Fe{sup 3+} moments. The field-induced spin-reorientation was detected on YFeO{sub 3} and was gradually suppressed by Lu{sup 3+} doping. Polarization hysteresis loops of Y{sub 1-x}Lu{sub x}FeO{sub 3} (0 {<=} x {<=} 1) were observed at room temperature. Our results suggest that the multiferroic properties may exist in the Y{sub 1-x}Lu{sub x}FeO{sub 3} (0 {<=} x {<=} 1) ceramics.

  16. Mössbauer studies of superparamagnetism in E. coli

    NASA Astrophysics Data System (ADS)

    Hawkins, C.; Williams, J. M.

    1992-02-01

    Proteins containing magnetic cores and combining the properties of cytochrome b 1 with those of ferritin have been isolated from bacterial sources such as Azotobacter vinelandii and Escherichia coli. The similarity with ferritin is supported by electron microscopy in which the imaged molecules appear spherical with an electron opaque core and an electron transparent shell. The small particle sizes of such iron containing cores normally leads to the observation of superparamagnetism with blocking temperatures in the range 20-50 K when investigated by Mössbauer spectroscopy. However, earlier work on E. coli indicated that in these samples no superparamagnetism is observed. Instead they found a magnetic ordering temperature of only 3.5 K with quadrupole doublets observed at higher temperatures. In this 57Fe Mössbauer investigation of E. coli, however, we do observe superparamagnetic behaviour consistent with that found in other forms of ferritin and these new results will be presented and discussed.

  17. Non-Heme Iron Absorption and Utilization from Typical Whole Chinese Diets in Young Chinese Urban Men Measured by a Double-Labeled Stable Isotope Technique

    PubMed Central

    Yang, Lichen; Zhang, Yuhui; Wang, Jun; Huang, Zhengwu; Gou, Lingyan; Wang, Zhilin; Ren, Tongxiang; Piao, Jianhua; Yang, Xiaoguang

    2016-01-01

    Background This study was to observe the non-heme iron absorption and biological utilization from typical whole Chinese diets in young Chinese healthy urban men, and to observe if the iron absorption and utilization could be affected by the staple food patterns of Southern and Northern China. Materials and Methods Twenty-two young urban men aged 18–24 years were recruited and randomly assigned to two groups in which the staple food was rice and steamed buns, respectively. Each subject received 3 meals containing approximately 3.25 mg stable 57FeSO4 (the ratio of 57Fe content in breakfast, lunch and dinner was 1:2:2) daily for 2 consecutive days. In addition, approximately 2.4 mg 58FeSO4 was administered intravenously to each subject at 30–60 min after dinner each day. Blood samples were collected from each subject to measure the enrichment of the 57Fe and 58Fe. Fourteen days after the experimental diet, non-heme iron absorption was assessed by measuring 57Fe incorporation into red blood cells, and absorbed iron utilization was determined according to the red blood cell incorporation of intravenously infused 58Fe SO4. Results Non-heme iron intake values overall, and in the rice and steamed buns groups were 12.8 ±2.1, 11.3±1.3 and 14.3±1.5 mg, respectively; the mean 57Fe absorption rates were 11±7%, 13±7%, and 8±4%, respectively; and the mean infused 58Fe utilization rates were 85±8%, 84±6%, and 85±10%, respectively. There was no significantly difference in the iron intakes, and 57Fe absorption and infused 58Fe utilization rates between rice and steamed buns groups (all P>0.05). Conclusion We present the non-heme iron absorption and utilization rates from typical whole Chinese diets among young Chinese healthy urban men, which was not affected by the representative staple food patterns of Southern and Northern China. This study will provide a basis for the setting of Chinese iron DRIs. PMID:27099954

  18. Characterization of iron in airborne particulate matter

    NASA Astrophysics Data System (ADS)

    Tavares, F. V. F.; Ardisson, J. D.; Rodrigues, P. C. H.; Brito, W.; Macedo, W. A. A.; Jacomino, V. M. F.

    2014-01-01

    In this work soil samples, iron ore and airborne atmospheric particulate matter (PM) in the Metropolitan Region of Belo Horizonte (MRBH), State of Minas Gerais, Brazil, are investigated with the aim of identifying if the sources of the particulate matter are of natural origin, such as, resuspension of particles from soil, or due to anthropogenic origins from mining and processing of iron ore. Samples were characterized by powder X-ray diffraction, X-ray fluorescence and 57Fe-Mössbauer spectroscopy. The results showed that soil samples studied are rich in quartz and have low contents of iron mainly iron oxide with low crystallinity. The samples of iron ore and PM have high concentration of iron, predominantly well crystallized hematite. 57Fe-Mössbauer spectroscopy confirmed the presence of similar iron oxides in samples of PM and in the samples of iron ore, indicating the anthropogenic origin in the material present in atmosphere of the study area.

  19. Mössbauer study of metallic iron and iron oxide nanoparticles having environmental purifying ability

    NASA Astrophysics Data System (ADS)

    Kubuki, Shiro; Watanabe, Yuka; Akiyama, Kazuhiko; Ristić, Mira; Krehula, Stjepko; Homonnay, Zoltán; Kuzmann, Ernő; Nishida, Tetsuaki

    2014-10-01

    A relationship between local structure and methylene blue (MB) decomposing ability of nanoparticles (NPs) of metallic iron ( Fe0) and maghemite (γ- Fe2O3) was investigated by 57Fe Mössbauer spectroscopy, X-ray diffractometry and UV-visible light absorption spectroscopy. γ- Fe2O3 NPs were successfully prepared by mixing ( NH4)2Fe ( SO4)2ṡ6H2O (Mohr's salt) and ( NH4)3Fe ( C2O4)3ṡ3H2O aqueous solution at 30 °C for 1 h, while those of Fe0 were obtained by the reduction of Mohr's salt with NaBH4. From the Scherrer's equation, the smallest crystallite sizes of γ- Fe2O3 NPs and Fe0 NPs were determined to be 9.7 and 1.5 nm, respectively. 57Fe Mössbauer spectrum of γ- Fe2O3 NPs consists of a relaxed sextet with isomer shift (δ) of 0.33±0.01 mm s-1, internal magnetic field (Hint) of 25.8±0.5 T, and linewidth (Γ) of 0.62±0.04 mm s-1. 57Fe Mössbauer spectrum of Fe0 NP is mainly composed of a sextet having δ, Δ, and Hint of 0.00±0.01 mm s-1 0.45±0.01 mm s-1, and 22.8±0.1 T, respectively. A bleaching test of the mixture of Fe0 and γ- Fe2O3 NPs (3:7 ratio, 100 mg) in MB aqueous solution (20 mL) for 6 h showed a remarkable decrease of MB concentration with the first-order rate constant (kMB) of 6.7 × 10-1 h-1. This value is larger than that obtained for the bleaching test using bulk Fe0+γ- Fe2O3 (3:7) mixture (kMB= 6.5×10-3h-1) . These results prove that MB decomposing ability is enhanced by the NPs mixture of Fe0 and γ- Fe2O3.

  20. Origin of magnetic and dielectric response in single phase nano crystalline BiFeO3

    NASA Astrophysics Data System (ADS)

    Feroze, Asad; Idrees, Muhammad; Nadeem, Muhammad; Siddiqi, Saadat A.; Saleem, Murtaza; Atif, Muhammad; Siddique, Muhammad; Shaukat, Saleem F.

    2016-12-01

    Stoichiometric and single phase synthesis of BiFeO3 is critical both in its particle industrial applications as well as in understanding the origin of its attractive dielectric and magnetic properties. In this study, BiFeO3 has been obtained at temperatures as low as 400 °C. Zero Fe+2/Fe+3 ratio, and absence of bismuth and oxygen non-stoichiometry have been probed by 57Fe Mössbauer spectroscopy. The appearance of different magnetic phases in 57Fe Mössbauer spectrum, MH hysteresis curve and exchange bias effect have been conferred on the basis of magneto-crystalline anisotropy and particle size distribution. Dependence of the dielectric response on the applied electric field reveals that the colossal dielectric response in BiFeO3 is dominated by extrinsic effects at grain-grain interface.

  1. Mössbauer spectra obtained using β - γ coincidence method after 57Mn implantation into LiH and LiD

    NASA Astrophysics Data System (ADS)

    Sato, Y.; Kobayashi, Y.; Yamada, Y.; Kubo, M. K.; Mihara, M.; Nagatomo, T.; Sato, W.; Miyazaki, J.; Tanigawa, S.; Natori, D.; Sato, S.; Kitagawa, A.

    2016-12-01

    Highly energetic 57Mn ( T 1/2 = 1.45 m) was generated by nuclear projectile fragmentation in a heavy-ion accelerator, and implanted into lithium hydride (LiH) and lithium deuteride (LiD) at 578 K. Mössbauer spectroscopy with β - γ coincidence detection was then carried out on the 57Fe obtained from β -decay of the 57Mn to study the time dependence of the site distributions and coordination environments of dilute Fe atoms implanted in the LiH and LiD. The results suggest that the Fe atoms can substitute for either the Li and H or D atoms within 100 ns. Additionally, the displacement behavior of the substitutional 57Fe atoms on the lattice sites is discussed.

  2. Stroboscopic detection of nuclear resonance in an arbitrary scattering channel.

    PubMed

    Deák, L; Bottyán, L; Callens, R; Coussement, R; Major, M; Nasu, S; Serdons, I; Spiering, H; Yoda, Y

    2015-03-01

    The theory of heterodyne/stroboscopic detection of nuclear resonance scattering is developed, starting from the total scattering matrix as a product of the matrix of the reference sample and the sample under study. This general approach holds for all dynamical scattering channels. In the forward channel, which has been discussed in detail in the literature, the electronic scattering manifests itself only in an energy-independent diminution of the scattered intensity. In all other channels, complex resonance line shapes of the heterodyne/stroboscopic spectra are encountered, as a result of the interference of electronic and nuclear scattering. The grazing-incidence case will be evaluated and described in detail. Experimental data of classical X-ray reflectivity and their stroboscopically detected resonant counterpart spectra on the [(nat)Fe/(57)Fe]10 isotope periodic multilayer and antiferromagnetic [(57)Fe/Cr]20 superlattice are fitted simultaneously.

  3. Iron deficiency, but not anemia, upregulates iron absorption in breast-fed peruvian infants.

    PubMed

    Hicks, Penni D; Zavaleta, Nelly; Chen, Zhensheng; Abrams, Steven A; Lönnerdal, Bo

    2006-09-01

    Iron absorption in adults is regulated by homeostatic mechanisms that decrease absorption when iron status is high. There are few data, however, regarding the existence of a similar homeostatic regulation in infants. We studied 2 groups of human milk-fed infants using (57)Fe (given as ferrous sulfate without any milk) and (58)Fe (given at the time of a breast-milk feeding) stable isotopes to determine whether healthy infants at risk for iron deficiency would regulate their iron absorption based on their iron status. We studied 20 Peruvian infants at 5-6 mo of age and 18 infants at 9-10 mo of age. We found no effect of infant hemoglobin concentration on iron absorption with 5-6 mo-old infants absorbing 19.2 +/- 2.1% and 9- to 10-mo-old infants absorbing 25.8 +/- 2.6% of the (57)Fe dose. For (58)Fe, 5- to 6-mo-old infants absorbed 42.6 +/- 5.0% and 9 to 10-mo-old infants absorbed 51.9 +/- 10.3%. Following log transformation, iron absorption from (57)Fe (r = -0.61, P = < 0.001) and (58)Fe (r = -0.61, P = < 0.001) were inversely correlated to serum ferritin (S-Ft). For both the (57)Fe and (58)Fe doses, infants with S-Ft <12 mg/L (n = 11) had significantly higher iron absorption than those with S-Ft >12 mg/L. We concluded that iron absorption in infants is related to iron status as assessed by serum ferritin but not hemoglobin concentration. Infants with low iron status upregulate iron absorption from breast milk at both 5-6 and 9-10 mo of age.

  4. A Calorimetric Study of Almandine: Are the Thermodynamic Properties of the End-Member Aluminosilicate Garnets Finally Known Quantitatively?

    NASA Astrophysics Data System (ADS)

    Dachs, E.; Geiger, C. A.; Benisek, A.

    2012-12-01

    The aluminosilicate garnets (E3Al2Si3O12 with E = Fe2+, Mn2+, Ca, Mg) form an important rock-forming mineral group. Much study has been directed toward determining their thermodynamic properties. The iron end-member almandine (Fe3Al2Si3O12) is a key phase in many petrologic investigations. As part of an ongoing calorimetric and thermodynamic study of the aluminosilicate garnets, the heat capacity of three synthetic well-characterized polycrystalline almandine garnets and one natural almandine-rich single crystal was measured. The various garnets were characterized by optical microscopy, electron-microprobe analysis, X-ray powder diffraction and 57Fe Mössbauer spectroscopy. Heat capacity measurements were performed in the temperature range 3 to 300 K using relaxation calorimetry and between 282 and 764 K using DSC methods. From the former, So values between 336.7 ± 0.8 and 337.8 ± 0.8 J/molK are calculated for the different samples. The smaller value is considered the best So for end-member stoichiometric almandine, because it derives from the "best" Fe3+-free synthetic sample. The Cp behavior for almandine at T > 298 K is given by the polynomial (in J/molK): Cp = 649.06(±4) - 3837.57(±122)T-0.5 - 1.44682(±0.06)107T-2 + 1.94834(±0.09)109T-3, which is calculated using DSC data together with one published heat-content datum determined by transposed-drop calorimetry along with a new determination that gives H1181K - H302K = 415.0 ± 3.2 kJ/mole. Almandine shows a λ-type heat-capacity anomaly at low temperatures resulting from a paramagnetic-antiferromagnetic phase transition at about 9 K. The lattice heat capacity was calculated using the single-parameter phonon dispersion model of Komada and Westrum (1997), which allows the non-lattice heat capacity (Cex) behavior to be modelled. An analysis shows the presence of an electronic heat-capacity contribution (Cel - Schottky anomaly) around 17 K that is superimposed on a larger magnetic heat-capacity effect (Cmag

  5. CEMS study of defect annealing in Fe implanted AlN

    NASA Astrophysics Data System (ADS)

    Bharuth-Ram, K.; Geburt, S.; Ronning, C.; Masenda, H.; Naidoo, D.

    2016-12-01

    An AlN thin film grown on sapphire substrate was implanted with 45 keV 57Fe and 56Fe ions at several energies to achieve a homogeneous concentration profile of approximately 2.6 at.%. in the AlN film. Conversion electron Mössbauer Spectroscopy data were collected after annealing the sample up to 900 °C. The spectra were fitted with three components, a single line attributed to small Fe clusters, and two quadrupole split doublets attributed to Fe substituting Al in the wurtzite AlN lattice and to Fe located in implantation induced lattice damage. The damage component shows significant decrease on annealing up to 900 °C, accompanied by corresponding increases in the singlet component and the substitutional Fe.

  6. Local structure study of Fe dopants in Ni-deficit Ni3Al alloys

    DOE PAGES

    V. N. Ivanovski; Umicevic, A.; Belosevic-Cavor, J.; ...

    2015-08-24

    We found that the local electronic and magnetic structure, hyperfine interactions, and phase composition of polycrystalline Ni–deficient Ni 3-x FexAl (x = 0.18 and 0.36) were investigated by means of 57 Fe Mössbauer spectroscopy. The samples were characterized by X–ray diffraction and magnetization measurements. The ab initio calculations performed with the projector augmented wave method and the calculations of the energies of iron point defects were done to elucidate the electronic structure and site preference of Fe doped Ni 3 Al. Moreover, the value of calculated electric field gradient tensor Vzz=1.6 1021Vm-2 matches well with the results of Mössbauer spectroscopymore » and indicates that the Fe atoms occupy Ni sites.« less

  7. Mössbauer study of the effect of rare earth substitution into montmorillonite

    NASA Astrophysics Data System (ADS)

    Kuzmann, E.; Singh, L. H.; Garg, V. K.; de Oliveira, A. C.; Kovács, E. M.; Molnár, Á. M.; Homonnay, Z.; Kónya, P.; Nagy, N. M.; Kónya, J.

    2016-12-01

    Novel montmorillonites were prepared by the exchange of the interlayer cations with a series of rare earth cations (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, and Er) and characterized by XRD, XRF, SEM, chemical analysis and 57Fe Mössbauer spectroscopy. An unexpected magnetically split component, assigned to iron being in the interlayer space, was observed in the Mössbauer spectra at 78K in some rare earth cation exchanged montmorillonite. This paper is the initial report about this observation. The transition of iron from the octahedral site to the interlayer and possible incorporation of rare earths in sites different from those which are in the interlayer space was concluded.

  8. APPLICATION OF 129I MOSSBAUER EFFECT TO BIOLOGICAL SYSTEMS: STUDIES WITH HEME MODELS*

    PubMed Central

    Pasternak, M.; Debrunner, Peter G.; DePasquali, G.; Hager, Lowell P.; Yeoman, L.

    1970-01-01

    The Mossbauer effect associated with 129I, 125Te, and 57Fe has been applied to investigate structural properties of the axial ligands in ferric-high spin hematoheme-I, hematoheme-Te, and hematoheme-histidine-iodide. The magnitude and sign of the 129I quadrupole coupling constant (e2qQ) and the isomer shift, as deduced from the Mossbauer effect spectra, are consistent with an axial, s-p hybridized bond of overwhelming σ-character. Identical coupling constant (e2qQ(127I) = -1826 ± 3 MHz) were measured for both heme-I and hematoheme-histidine-iodide. Implications of this result to the nature of ferric-high spin heme-histidine complexing are discussed. A stable heme 125Te species formed in the electron-capture decay of heme-125I is observed, and structural properties of this singly bonded telluride ligand are discussed. PMID:16591848

  9. Non-traditional stable isotope behaviors in immiscible silica-melts in a mafic magma chamber

    PubMed Central

    Zhu, Dan; Bao, Huiming; Liu, Yun

    2015-01-01

    Non-traditional stable isotopes have increasingly been applied to studies of igneous processes including planetary differentiation. Equilibrium isotope fractionation of these elements in silicates is expected to be negligible at magmatic temperatures (δ57Fe difference often less than 0.2 per mil). However, an increasing number of data has revealed a puzzling observation, e.g., the δ57Fe for silicic magmas ranges from 0‰ up to 0.6‰, with the most positive δ57Fe almost exclusively found in A-type granitoids. Several interpretations have been proposed by different research groups, but these have so far failed to explain some aspects of the observations. Here we propose a dynamic, diffusion-induced isotope fractionation model that assumes Si-melts are growing and ascending immiscibly in a Fe-rich bulk magma chamber. Our model offers predictions on the behavior of non-traditional stable isotope such as Fe, Mg, Si, and Li that are consistent with observations from many A-type granitoids, especially those associated with layered intrusions. Diffusion-induced isotope fractionation may be more commonly preserved in magmatic rocks than was originally predicted. PMID:26620121

  10. Non-traditional stable isotope behaviors in immiscible silica-melts in a mafic magma chamber.

    PubMed

    Zhu, Dan; Bao, Huiming; Liu, Yun

    2015-12-01

    Non-traditional stable isotopes have increasingly been applied to studies of igneous processes including planetary differentiation. Equilibrium isotope fractionation of these elements in silicates is expected to be negligible at magmatic temperatures (δ(57)Fe difference often less than 0.2 per mil). However, an increasing number of data has revealed a puzzling observation, e.g., the δ(57)Fe for silicic magmas ranges from 0‰ up to 0.6‰, with the most positive δ(57)Fe almost exclusively found in A-type granitoids. Several interpretations have been proposed by different research groups, but these have so far failed to explain some aspects of the observations. Here we propose a dynamic, diffusion-induced isotope fractionation model that assumes Si-melts are growing and ascending immiscibly in a Fe-rich bulk magma chamber. Our model offers predictions on the behavior of non-traditional stable isotope such as Fe, Mg, Si, and Li that are consistent with observations from many A-type granitoids, especially those associated with layered intrusions. Diffusion-induced isotope fractionation may be more commonly preserved in magmatic rocks than was originally predicted.

  11. Large iron isotope fractionation at the oxic-anoxic boundary in Lake Nyos

    NASA Astrophysics Data System (ADS)

    Teutsch, Nadya; Schmid, Martin; Müller, Beat; Halliday, Alex N.; Bürgmann, Helmut; Wehrli, Bernhard

    2009-07-01

    The degassing of volcanic Lake Nyos (Cameroon) provides the opportunity to study the strong isotopic variation of dissolved Fe(II) in a well constrained redox cycle and to identify the governing processes by reaction-transport modeling. Two depth profiles sampled in the lake in March 2004 and 2005 reveal an increase in iron concentrations and δ57Fe from around 1 mg L - 1 and - 1.88‰ at 55 m depth up to 344 mg L - 1 and + 0.83‰ at the bottom of the lake, respectively. A steep increase in δ57Fe was observed across the oxic-anoxic boundary. As many biological and geochemical processes are known to fractionate Fe isotopes, we used a calibrated reaction-transport model to disentangle the processes governing the Fe cycle. The model combines the isotopic signatures of dissolved Fe(II) and settling Fe(III) particles with the concentration profiles and settling fluxes of the Fe particles in the lake. We show that the strong shift in δ57Fe is caused by isotopic fractionation via dissimilatory Fe reduction across the oxic-anoxic boundary of Lake Nyos. The shift towards more positive values below the oxic-anoxic interface could be attributed to vertical mixing of a heavier component from the bottom of the lake.

  12. Non-traditional stable isotope behaviors in immiscible silica-melts in a mafic magma chamber

    NASA Astrophysics Data System (ADS)

    Zhu, Dan; Bao, Huiming; Liu, Yun

    2015-12-01

    Non-traditional stable isotopes have increasingly been applied to studies of igneous processes including planetary differentiation. Equilibrium isotope fractionation of these elements in silicates is expected to be negligible at magmatic temperatures (δ57Fe difference often less than 0.2 per mil). However, an increasing number of data has revealed a puzzling observation, e.g., the δ57Fe for silicic magmas ranges from 0‰ up to 0.6‰, with the most positive δ57Fe almost exclusively found in A-type granitoids. Several interpretations have been proposed by different research groups, but these have so far failed to explain some aspects of the observations. Here we propose a dynamic, diffusion-induced isotope fractionation model that assumes Si-melts are growing and ascending immiscibly in a Fe-rich bulk magma chamber. Our model offers predictions on the behavior of non-traditional stable isotope such as Fe, Mg, Si, and Li that are consistent with observations from many A-type granitoids, especially those associated with layered intrusions. Diffusion-induced isotope fractionation may be more commonly preserved in magmatic rocks than was originally predicted.

  13. Low temperature behavior of hyperfine fields in amorphous and nanocrystalline FeMoCuB

    SciTech Connect

    Kohout, Jaroslav; Křišt'an, Petr; Kubániová, Denisa; Kmječ, Tomáš; Závěta, Karel; Štepánková, Helena; Lančok, Adriana; Sklenka, L'ubomír; Matúš, Peter; and others

    2015-05-07

    Low temperature (4.2 K) magnetic behavior of Fe{sub 76}Mo{sub 8}Cu{sub 1}B{sub 15} metallic glass was studied by {sup 57}Fe Mössbauer spectrometry (MS) and {sup 57}Fe NMR. Distributions of hyperfine magnetic fields P(B) were determined for as-quenched and annealed (nanocrystalline) samples with relative fraction of the grains about 43%. P(B) distributions were derived for both the amorphous matrix and nanocrystalline grains. NMR of alloys with natural and {sup 57}Fe enriched Fe enabled to assess the contribution of {sup 11}B to the total NMR signal. P(B) distribution of the as-quenched alloy derived from MS matches reasonably well the one from NMR of the enriched sample. NMR signal from the sample with natural Fe exhibits contributions from {sup 11}B nuclei. The principal NMR lines of the annealed alloys at 47 MHz correspond to bcc Fe nanocrystals. Small asymmetry of the lines towards higher frequencies might be an indication of possible impurity atoms in the bcc structure. The observed differences between natural and enriched samples are attributed to higher sensitivity in the latter. Positions of the lines attributed to bcc Fe nanocrystals obtained from MS and NMR are in perfect agreement.

  14. FeSi diffusion barriers in Fe/FeSi/Si/FeSi/Fe multilayers and oscillatory antiferromagnetic exchange coupling

    NASA Astrophysics Data System (ADS)

    Stromberg, F.; Bedanta, S.; Antoniak, C.; Keune, W.; Wende, H.

    2008-10-01

    We study the diffusion of 57Fe probe atoms in Fe/FeSi/Si/FeSi/Fe multilayers on Si(111) prepared by molecular beam epitaxy by means of 57Fe conversion electron Mössbauer spectroscopy (CEMS). We demonstrate that the application of FeSi boundary layers successfully inhibits the diffusion of 57Fe into the Si layer. The critical thickness for the complete prevention of Fe diffusion takes place at a nominal FeSi thickness of tFeSi = 10-12 Å, which was confirmed by the evolution of the isomer shift δ of the crucial CEM subspectrum. The formation of the slightly defective c-FeSi phase for thicker FeSi boundary layers (~20 Å) was confirmed by CEMS and reflection high-energy electron diffraction (RHEED). Ferromagnetic resonance (FMR) shows that, for tFeSi = 0-14 Å, the Fe layers in all samples are antiferromagnetically coupled and we observe an oscillatory antiferromagnetic coupling strength with FMR and superconducting quantum interference device (SQUID) magnetometry for varying FeSi thickness with a period of ~6 Å.

  15. Growth of ultra-thin FeO(100) films on Ag(100): A combined XPS, LEED and CEMS study

    NASA Astrophysics Data System (ADS)

    Abreu, G. J. P.; Paniago, R.; Pfannes, H.-D.

    2014-01-01

    The production and characterization of ultra-thin iron oxide films grown on an atomically clean Ag(100) surface by molecular beam epitaxy (MBE) is presented. The goal of this work was to prepare ultra-thin FeO(100) with excellent crystallographic quality. The films were prepared with high purity 57Fe and O2 and afterwards analyzed in situ by means of Low Energy Electron Diffraction (LEED), X-Ray Photoelectron Spectroscopy (XPS) and Conversion Electron Mössbauer Spectroscopy (CEMS). During preparation the evaporation rate, the O2 partial pressure, film thickness and annealing procedures were varied. The analysis of the various samples showed that in general a mixture of FeO and Fe3O4 phases is obtained. We determined the best conditions to produce the desired oxide (FeO). Besides the paramagnetic phase, the antiferromagnetic phase of the FeO films was characterized by low temperature Mössbauer spectra.

  16. Mössbauer spectroscopic study on spin crossover coordination polymer Fe(3-Clpy)2[Pd(CN)4

    NASA Astrophysics Data System (ADS)

    Kitazawa, Takafumi; Sekiya, Madoka; Kawasaki, Takeshi; Takahashi, Masashi

    2016-12-01

    57Fe Mössbauer spectroscopic results on the alternatively prepared spin crossover coordination polymer Fe(3-Clpy)2Pd(CN)4 sample I agree with those of SQUID data. Mössbauer specrum at RT shows two diffrent doublets which correspond to the HS1(inner doublet) and HS2(outer doublet). The intensity of the HS1 doublet decreases on cooling to 78 K at the expense of a new one featuring the LS singlet. Almost 100 % of HS1 change to LS singlet due to iron(II) ions coordinated by four N atoms of cyano groups and two N atoms of 3-Clpy ligand in the sample I. The SQUID data of the sample I prepared by a new direct contact method are different from those of the already reported Fe(3-Clpy)2Pd(CN)4 sample. The differences of the SQUID data are associated with particle size effects in molecule spin crossover samples.

  17. Abiotic U(VI) Reduction by Sorbed Fe(II) on Natural Sediments

    SciTech Connect

    Fox, Patricia M.; Davis, James A.; Kukkadapu, Ravi K.; Singer, David M.; Bargar, John R.; Williams, Kenneth H.

    2013-09-15

    Laboratory experiments were performed as a function of aqueous Fe(II) concentration to determine the uptake and oxidation of Fe(II), and Fe(II)-mediated abiotic reduction of U(VI) by aquifer sediments from the Rifle IFRC field site in Colorado, USA. Mössbauer analysis of the sediments spiked with aqueous 57Fe(II) showed that 57Fe(II) was oxidized on the mineral surfaces to 57Fe(III) and most likely formed a nano-particulate Fe(III)-oxide or ferrihydrite-like phase. The extent of 57Fe oxidation decreased with increasing 57Fe(II) uptake, such that 100 % was oxidized at 7.3 μmol/g Fe and 52 % at 39.6 μmol/g Fe, indicating that the sediments had a finite capacity for oxidation of Fe(II). Abiotic U(VI) reduction was observed by XANES spectroscopy only when the Fe(II) uptake was greater than approximately 20 μmol/g and surface-bound Fe(II) was present. The level of U(VI) reduction increased with increasing Fe(II)- loading above this level to a maximum of 18 and 36 % U(IV) at pH 7.2 (40.7 μmol/g Fe) and 8.3 (56.1 μmol/g Fe), respectively in the presence of 400 ppm CO2. Greater U(VI) reduction was observed in CO2 free systems [up to 44 and 54 % at pH 7.2 (17.3 μmol/g Fe) and 8.3 (54.8 μmol/g Fe), respectively] compared to 400 ppm CO2 systems, presumably due to differences in aqueous U(VI) speciation. While pH affects the amount of Fe(II) uptake onto the solid phase, with greater Fe(II) uptake at higher pH, similar amounts of U(VI) reduction were observed at pH 7.2 and 8.3 for a similar Fe(II) uptake. Thus, it appears that abiotic U(VI) reduction is controlled primarily by Fe(II) concentration and aqueous U(VI) speciation. The range of Fe(II) loadings tested in this study are within the range observed in bioreduced sediments, suggesting that Fe(II)-mediated abiotic U(VI) reduction may indeed play a role in field settings.

  18. Abiotic U(VI) reduction by sorbed Fe(II) on natural sediments

    NASA Astrophysics Data System (ADS)

    Fox, Patricia M.; Davis, James A.; Kukkadapu, Ravi; Singer, David M.; Bargar, John; Williams, Kenneth H.

    2013-09-01

    Laboratory experiments were performed as a function of aqueous Fe(II) concentration to determine the uptake and oxidation of Fe(II), and Fe(II)-mediated abiotic reduction of U(VI) by aquifer sediments from the DOE Rifle field research site in Colorado, USA. Mössbauer analysis of the sediments spiked with aqueous 57Fe(II) showed that 57Fe(II) was oxidized on the mineral surfaces to 57Fe(III) and most likely formed a nano-particulate Fe(III)-oxide or ferrihydrite-like phase. The extent of 57Fe oxidation decreased with increasing 57Fe(II) uptake, such that 98% was oxidized at 7.3 μmol/g Fe and 41% at 39.6 μmol/g Fe, indicating that the sediments had a limited capacity for oxidation of Fe(II). Abiotic U(VI) reduction was observed by XANES spectroscopy only when the Fe(II) uptake was greater than approximately 20 μmol/g and surface-bound Fe(II) was present, possibly as oligomeric Fe(II) surface species. The degree of U(VI) reduction increased with increasing Fe(II)-loading above this level to a maximum of 18% and 36% U(IV) at pH 7.2 (40.7 μmol/g Fe) and 8.3 (56.1 μmol/g Fe), respectively in the presence of 400 ppm CO2. Greater U(VI) reduction was observed in CO2-free systems [up to 44% and 54% at pH 7.2 (17.3 μmol/g Fe) and 8.3 (54.8 μmol/g Fe), respectively] compared to 400 ppm CO2 systems, presumably due to differences in aqueous U(VI) speciation. While pH affects the amount of Fe(II) uptake onto the solid phase, with greater Fe(II) uptake at higher pH, similar amounts of U(VI) reduction were observed at pH 7.2 and 8.3 for a similar Fe(II) uptake. Thus, it appears that abiotic U(VI) reduction is controlled primarily by sorbed Fe(II) concentration and aqueous U(VI) speciation. The range of Fe(II) loadings tested in this study are within the range observed in biostimulation experiments at the Rifle site, suggesting that Fe(II)-mediated abiotic U(VI) reduction could play a significant role in field settings.

  19. Microbial Reduction of Uranium under Iron- and Sulfate-reducing Conditions: Effect of Amended Goethite on Microbial Community Composition and Dynamics

    SciTech Connect

    Moon, Hee Sun; McGuinness, L.; Kukkadapu, Ravi K.; Peacock, Aaron D.; Komlos, John; Kerkhoff, Lee; Long, Philip E.; Jaffe, Peter R.

    2010-07-01

    There is a growing need for a better understanding of the biogeochemical dynamics involved in microbial U(VI) reduction due to an increasing interest in using biostimulation via electron donor addition as a means to remediate uranium contaminated sites. U(VI) reduction has been observed to be maximized during iron reducing conditions and to decrease upon commencement of sulfate reducing conditions. There are many unknowns regarding the impact of iron/sulfate biogeochemistry on U(VI) reduction. This includes Fe(III) availability as well as the microbial community changes, including the activity of iron-reducers during the uranium biostimulation period even after the onset of sulfate reduction. Up-flow column experiments were conducted with Old Rifle site sediments containing Fe-oxides, Fe-clays, and sulfate rich groundwater. Half of the columns had sediment that was augmented with small amounts of small-particle 57Fe-goethite to track continuously minute goethite changes, and to study the effects of increased Fe(III) levels on the overall biostimulation dynamics. The addition of the 57Fe-goethite did not delay the onset of sulfate reduction, but slightly suppressed the overall rate of sulfate reduction and hence acetate utilization, it did not affect the bacterial numbers of Geobacter-like species throughout the experiment, but did lower the numbers of sulfate reducers in the sediments. 57Fe-Mössbauer analyses (a 57Fe-specific technique) confirmed that there was bioavailable iron present after the onset of sulfate reduction and that iron was still being reduced during sulfate reduction. Addition of the 57Fe-goethite to the sediment had a noticeable effect on the overall composition of the microbial population. 16S rRNA analyses of biostimulated sediment using TRFLP (terminal restriction fragment length polymorphism) showed that Geobacter sp. (a known Fe-reducer) was still active and replicating during the period of significant sulfate reduction. DNA fingerprints of

  20. Copper stable isotopes as tracers of metal-sulphide segregation and fractional crystallisation processes on iron meteorite parent bodies

    NASA Astrophysics Data System (ADS)

    Williams, Helen M.; Archer, Corey

    2011-06-01

    We report high precision Cu isotope data coupled with Cu concentration measurements for metal, troilite and silicate fractions separated from magmatic and non-magmatic iron meteorites, analysed for Fe isotopes (δ 57Fe; permil deviation in 57Fe/ 54Fe relative to the pure iron standard IRMM-014) in an earlier study ( Williams et al., 2006). The Cu isotope compositions (δ 65Cu; permil deviation in 65Cu/ 63Cu relative to the pure copper standard NIST 976) of both metals (δ 65Cu M) and sulphides (δ 65Cu FeS) span much wider ranges (-9.30 to 0.99‰ and -8.90 to 0.63‰, respectively) than reported previously. Metal-troilite fractionation factors (Δ 65Cu M-FeS = δ 65Cu M - δ 65Cu FeS) are variable, ranging from -0.07 to 5.28‰, and cannot be explained by equilibrium stable isotope fractionation coupled with either mixing or reservoir effects, i.e. differences in the relative proportions of metal and sulphide in the meteorites. Strong negative correlations exist between troilite Cu and Fe (δ 57Fe FeS) isotope compositions and between metal-troilite Cu and Fe (Δ 57Fe M-FeS) isotope fractionation factors, for both magmatic and non-magmatic irons, which suggests that similar processes control isotopic variations in both systems. Clear linear arrays between δ 65Cu FeS and δ 57Fe FeS and calculated Cu metal-sulphide partition coefficients (D Cu = [Cu] metal/[Cu] FeS) are also present. A strong negative correlation exists between Δ 57Fe M-FeS and D Cu; a more diffuse positive array is defined by Δ 65Cu M-FeS and D Cu. The value of D Cu can be used to approximate the degree of Cu concentration equilibrium as experimental studies constrain the range of D Cu between Fe metal and FeS at equilibrium to be in the range of 0.05-0.2; D Cu values for the magmatic and non-magmatic irons studied here range from 0.34 to 1.11 and from 0.04 to 0.87, respectively. The irons with low D Cu values (closer to Cu concentration equilibrium) display the largest Δ 57Fe M-FeS and the

  1. Nature and Reactivity of Sediment-Associated Spiked Fe(II) Toward Abiotic Uranium Reduction

    NASA Astrophysics Data System (ADS)

    Kukkadapu, R.; Fox, P. M.; Davis, J.

    2011-12-01

    Uranium (U) is a priority contaminant at U.S. Department of Energy Uranium Mill Tailings Remedial Action (UMTRA) sites. Mobility of U in contaminated aquifers is governed by a complex assortment of site-specific biogeochemical and hydrological properties, sediment Fe-mineralogy, and redox status. There is a particular interest in understanding factors governing U attenuation to Fe-mineralogy under natural conditions. Thus, the goal of this work is to investigate geochemical effects of Fe redox state on U mobility under conditions relevant to the Rifle aquifer, an UMTRA site. Particularly, the focus is to gain insights into the degree and mechanism of Fe(II) uptake by Rifle sediments that exhibit complex Fe-mineralogy composed of various Fe-oxides and Fe-containing clays and on the possibility of abiotic U(VI) reduction by adsorbed Fe(II) and secondary Fe(II) minerals. Earlier field studies where Fe(II)-amended groundwater was injected into the Rifle aquifer indicated: a) Fe(II) uptake by Rifle sediments is extensive and b) abiotic U(VI) reduction by Fe(II) may be important at pH 8.3. Batch reactions between Rifle sediment and 57Fe(II) (57Fe isotope is a Mossbauer sensitive nuclide with a natural abundance of 2%) under conditions relevant to the Rifle aquifer indicated that, depending on the solution conditions: a) a large fraction of the spiked 57Fe(II) (55-100%) is oxidized to 57Fe(III) on sediment surfaces and, at pH 7.2, the degree of oxidation decreased as Fe(II) loading increased; b) the 57Fe(II)-oxidation is coupled to the transformation of an intrinsic ferrihydrite-like mineral to a nanoparticulate, Fe(II)/57Fe(III)-like mineral phase, and c) increasing pH from 7.2 to 8.3 and including carbonate in the medium has little or no effect on percent oxidation or mineral transformation. Preliminary X-ray absorption near edge structure (XANES) spectroscopy studies suggested that 20-30% of abiotic U(VI) reduction occurred, both at pH 7.2 and 8.3, in the sediments

  2. BiMnFe(2)O(6) a Polysynthetically Twinned hcp MO Structure

    SciTech Connect

    T Yang; A Abakumov; J Hadermann; G Van Tendeloo; I Nowik; P Stephens; J Hemberger; A Tsirlin; K Ramanujachary; et al.

    2011-12-31

    The most efficient use of spatial volume and the lowest potential energies in the metal oxide structures are based on cubic close packing (ccp) or hexagonal close packing (hcp) of anions with cations occupying the interstices. A promising way to tune the composition of close packed oxides and design new compounds is related to fragmenting the parent structure into modules by periodically spaced planar interfaces, such as twin planes at the unit cell scale. The unique crystal chemistry properties of cations with a lone electron pair, such as Bi{sup 3+} or Pb{sup 2+}, when located at interfaces, enables them to act as 'chemical scissors', to help relieve configurational strain. With this approach, we synthesized a new oxide, BiMnFe{sub 2}O{sub 6}, where fragments of the hypothetical hcp oxygen-based MO structure (the NiAs structure type), for the first time, serve as the building modules in a complex transition metal oxide. Mn{sup 3+} and Fe{sup 3+} ions are randomly distributed in two crystallographically independent sites (M1 and M2). The structure consists of quasi two-dimensional blocks of the 2H hexagonal close packed MO structure cut along the (114) crystal plane of the hcp lattice and stacked along the c axis. The blocks are related by a mirror operation that allows BiMnFe{sub 2}O{sub 6} to be considered as a polysynthetically twinned 2H hcp MO structure. The transition to an AFM state with an incommensurate spin configuration at {approx}212 K is established by {sup 57}Fe Moessbauer spectroscopy, magnetic susceptibility, specific heat and low temperature powder neutron diffraction.

  3. BiMnFe2O6 a Polysynthetically Twinned hcp MO Structure

    SciTech Connect

    T Yang; A Abakumov; J Hadermann; G Van Tendeloo; I Nowik; P Stephens; J Hemberger; M Croft; A Ignatov; et al.

    2011-12-31

    The most efficient use of spatial volume and the lowest potential energies in the metal oxide structures are based on cubic close packing (ccp) or hexagonal close packing (hcp) of anions with cations occupying the interstices. A promising way to tune the composition of close packed oxides and design new compounds is related to fragmenting the parent structure into modules by periodically spaced planar interfaces, such as twin planes at the unit cell scale. The unique crystal chemistry properties of cations with a lone electron pair, such as Bi{sup 3+} or Pb{sup 2+}, when located at interfaces, enables them to act as 'chemical scissors', to help relieve configurational strain. With this approach, we synthesized a new oxide, BiMnFe{sub 2}O{sub 6}, where fragments of the hypothetical hcp oxygen-based MO structure (the NiAs structure type), for the first time, serve as the building modules in a complex transition metal oxide. Mn{sup 3+} and Fe{sup 3+} ions are randomly distributed in two crystallographically independent sites (M1 and M2). The structure consists of quasi two-dimensional blocks of the 2H hexagonal close packed MO structure cut along the (114) crystal plane of the hcp lattice and stacked along the c axis. The blocks are related by a mirror operation that allows BiMnFe{sub 2}O{sub 6} to be considered as a polysynthetically twinned 2H hcp MO structure. The transition to an AFM state with an incommensurate spin configuration at {approx}212 K is established by {sup 57}Fe Moessbauer spectroscopy, magnetic susceptibility, specific heat and low temperature powder neutron diffraction.

  4. High pressure metallization of Mott Insulators: Magnetic, structural and electronic properties

    SciTech Connect

    Pasternak, M.P.; Hearne, G.; Sterer, E.; Taylor, R.D.; Jeanloz, R.

    1993-07-20

    High pressure studies of the insulator-metal transition in the (TM)I{sub 2} (TM = V, Fe, Co and Ni) compounds are described. Those divalent transition-metal iodides are structurally isomorphous and classified as Mott Insulators. Resistivity, X-ray diffraction and Moessbauer Spectroscopy were employed to investigate the electronic, structural, and magnetic properties as a function of pressure both on the highly correlated and on the metallic regimes.

  5. Superparamagnetic Particle Size Limit of Mn-Zn Ferrite Nanoparticles Synthesised Through Aqueous Method

    SciTech Connect

    Joseyphus, R. Justin; Narayanasamy, A.; Jeyadevan, B.; Shinoda, K.; Tohji, K.

    2006-05-15

    Mn0.67Zn0.33Fe2O4 nanoparticles with size ranging from 20 to 80 nm have been synthesized using the modified oxidation method. The Curie temperatures for all the samples are found to be within 630 {+-} 5 K suggesting that there is no size-dependent cation distribution. Moessbauer studies on the synthesized nanoparticles suggest that the critical particle size limit for superparamagnetism to be about 25 nm at 293 K.

  6. Growth of Ferrite Needles in Compacted Graphite Cast Iron

    SciTech Connect

    Duran, G.A.; Mercader, R.C.; Desimoni, J.; Perez, T.; Gregorutti, R.W.

    2005-04-26

    The austempering kinetics transformation of compacted graphite cast irons austempered at 623K is studied. The length (l) and the number per unit volume (N) of ferrite needles were followed by Scanning Electron Microscopy (SEM), while Moessbauer spectroscopy (MS) was used to determine the austenite relative areas. The SEM results are compared with theoretical calculations available in the literature and indicate that the diffusion of C atoms in austenite controls the transformation, confirming the indirect MS determinations.

  7. Mössbauer study of conductive oxide glass

    SciTech Connect

    Matsuda, Koken; Kubuki, Shiro; Nishida, Tetsuaki

    2014-10-27

    Heat treatment of barium iron vanadate glass, BaO‐Fe{sub 2}O{sub 3}‐V{sub 2}O{sub 5}, at temperatures higher than crystallization temperature causes a marked decrease in resistivity (ρ) from several MΩcm to several Ωcm. {sup 57}Fe Mössbauer spectrum of heat-treated vanadate glass shows a marked decrease in quadrupole splitting (Δ) of Fe{sup III}, reflecting a structural relaxation, i.e., an increased symmetry of 'distorted' FeO{sub 4} and VO{sub 4} tetrahedra which are connected to each other by sharing corner oxygen atoms. Structural relaxation of 3D-network of vanadate glass accompanies a decrease in the activation energy for the conduction, reflecting a decreased energy gap between the donor level and conduction band. A marked increase in the conductivity was observed in CuO- or Cu{sub 2}O-containing barium iron vanadate glass after heat treatment at 450 °C for 30 min or more. 'n-type semiconductor model combined with small polaron hopping theory' was proposed in order to explain the high conductivity.

  8. Spectral chemistry of green glass-bearing 15426 regolith

    NASA Technical Reports Server (NTRS)

    Burns, R. G.; Dyar, M. D.

    1983-01-01

    The detection of appreciable concentrations of ferric iron in a synthetic green glass equilibrated at an oxygen fugacity of 10 to the -11th atm prompted a Moessbauer spectral study of pristine emerald-green glass spherules carefully handpicked from regolith sample 15426. No Fe(3+) ions were detected in this lunar sample or in a synthetic green glass simulant equilibrated at fO2 = 10 to the -14th atm, suggesting that the green glass clods in rock 15426 formed under conditions of correspondingly low oxygen fugacities. The Moessbauer spectra indicated the presence of olivine crystallites in the lunar emerald green glass spherules. Measurements of homogeneous and partially devitrified synthetic silicate glasses revealed that significant changes of coordination environment about Fe(2+) ions in the glass structure occur during crystallization of olivine crystals from the melt.

  9. Spectral chemistry of green glass-bearing 15426 regolith

    NASA Technical Reports Server (NTRS)

    Burns, R. G.; Dyar, M. D.

    1983-01-01

    The detection of appreciable concentrations of ferric iron in a synthetic green glass equilibrated at an oxygen fugacity of 10 to the -11th atm prompted a Moessbauer spectral study of pristine emerald-green glass spherules carefully handpicked from regolith sample 15426. No Fe(3+) ions were detected in this lunar sample or in a synthetic green glass simulant equilibrated at fO2 = 10 to the -14th atm, suggesting that the green glass clods in rock 15426 formed under conditions of correspondingly low oxygen fugacities. The Moessbauer spectra indicated the presence of olivine crystallites in the lunar emerald green glass spherules. Measurements of homogeneous and partially devitrified synthetic silicate glasses revealed that significant changes of coordination environment about Fe(2+) ions in the glass structure occur during crystallization of olivine crystals from the melt.

  10. Effect of the Calcination Temperature on the Structural Properties and Catalytic Activity in the Fe/SiO2 System

    SciTech Connect

    Gallegos, Norma G.; Bengoa, Jose F.; Cagnoli, Maria V.; Alvarez, Ana M.; Marchetti, Sergio G.; Mercader, Roberto C.

    2005-04-26

    The structural properties of iron supported catalysts have strong influence on their activity and selectivity in the Fischer-Tropsch synthesis. We have studied the influence of the calcination temperature on the oxide-support interaction degree to reach the highest iron reducibility in Fe/SiO2 system to obtain the highest catalytic activity and selectivity. Silica was impregnated with an aqueous iron solution and it was calcined at 698, 898 and 1098 K. The three precursors were characterized by Moessbauer Spectroscopy, obtaining different iron oxide species on the support. They were reduced in H2 to produce three catalysts characterized by CO Chemisorption, Volumetric Oxidation and Moessbauer Spectroscopy. The activity and selectivity measurements showed that the calcination temperature increase led to a lower hydrocarbon production, a decrease of olefins production and an increase of methane.

  11. A Moessbauer spectrometer for the mineralogical analysis of the Mars surface: First temperature dependent tests of the detector and drive system

    NASA Technical Reports Server (NTRS)

    Held, P.; Teucher, R.; Klingelhoefer, G.; Foh, J.; Jaeger, H.; Kankeleit, E.

    1993-01-01

    Part of the scientific payload of the Mars-96 mission is a Fe-(57)Mossbauer (MB) spectrometer installed on a small rover to be placed on the surface of Mars. The instrument is under development at the University of Darmstadt. This instrument, with some modifications, is also included in the scientific payload of the proposed MARSNET mission of the European Space Agency (ESA). A similar instrument is currently under development in the US. The reason for developing a Mossbauer spectrometer for space applications is the high abundance of the element iron, especially on the surface of Mars. The elemental composition of Martian soil was determined during the Viking mission in 1976 but not it's mineralogical composition. One believes that it is composed mainly of iron-rich clay minerals, with an iron content of about 14 (plus or minus 2) wt-percent, partly magnetic. Of extremely great interest are the oxidation state of the iron, the magnetic phases and the mineral composition of the Mars surface. To these questions MB spectroscopy can provide important information, which are not available by other methods. We report on first tests of the experimental setup in the temperature range plus 20 C to -70 C, roughly corresponding to the temperature range on the surface of Mars. Also questions concerning the signal/noise ratio (S/N) are discussed.

  12. Comparison of Synchrotron MicroXANES Determination of Fe(3+)/Sigma Fe with Moessbauer Values for Clean Mineral Separates of Pyroxene from Martian Meteorites

    NASA Technical Reports Server (NTRS)

    Delaney, J. S.; Dyar, M. D.

    2003-01-01

    The oxidation state of Fe in Martian meteorites is a parameter of great interest and the ability to determine this value in micrometer scale samples is important. Intense, tunable x-ray sources at large synchrotron storage rings are being exploited to examine the Fe K-absorption edge with energy resolution of approx. 1-1.5eV in spots of 10x15 microns on thin sections of a wide variety of materials including several Martian meteorites. Synchrotron microXANES (SmX) spectroscopy is the technique that provides the most flexible capability for investigating Fe(3+)/Sigma Fe. Variation of Fe(3+)/Sigma Fe is manifested as a function of the energy of the pre-edge to the Fe absorption edge produced by the sample. SmX is at present the only technique that can be used with conventional polished thin sections. Data for a broad spectrum of minerals have been produced and indicate that SmX can be used with a large variety of samples types.

  13. In Situ Resource Utilization (ISRU) on the Moon: Moessbauer Spectroscopy as a Process Monitor for Oxygen Production. Results from a Field Test on Mauna Kea Volcano, Hawaii

    NASA Technical Reports Server (NTRS)

    Morris, R.V.; Schroder, C.; Graff, T.G.; Sanders, G.B.; Lee, K.A.; Simon, T.M.; Larson, W.E.; Quinn, J.W.; Clark, L.D.; Caruso, J.J.

    2009-01-01

    Essential consumables like oxygen must to be produced from materials on the lunar surface to enable a sustained, long-term presence of humans on the Moon. The Outpost Precursor for ISRU and Modular Architecture (OPTIMA) field test on Mauna Kea, Hawaii, facilitated by the Pacific International Space Center for Exploration Systems (PISCES) of the University of Hawaii at Hilo, was designed to test the implementation of three hardware concepts to extract oxygen from the lunar regolith: Precursor ISRU Lunar Oxygen Testbed (PILOT) developed by Lockheed Martin in Littleton, CO; Regolith & Environmental Science and Oxygen & Lunar Volatiles Extraction (RESOLVE) developed at the NASA Kennedy Space Center in Cape Canaveral, FL; and ROxygen developed at the NASA Johnson Space Center in Houston, TX. The three concepts differ in design, but all rely on the same general principle: hydrogen reduction of metal cations (primarily Fe2+) bonded to oxygen to metal (e.g., Fe0) with the production of water. The hydrogen source is residual hydrogen in the fuel tanks of lunar landers. Electrolysis of the water produces oxygen and hydrogen (which is recycled). We used the miniaturized M ssbauer spectrometer MIMOS II to quantify the yield of this process on the basis of the quantity of Fe0 produced. Iron M ssbauer spectroscopy identifies iron-bearing phases, determines iron oxidation states, and quantifies the distribution of iron between mineral phases and oxidation states. The oxygen yield can be calculated by quantitative measurements of the distribution of Fe among oxidation states in the regolith before and after hydrogen reduction. A M ssbauer spectrometer can also be used as a prospecting tool to select the optimum feedstock for the oxygen production plants (e.g., high total Fe content and easily reduced phases). As a demonstration, a MIMOS II backscatter spectrometer (SPESI, Germany) was mounted on the Cratos rover (NASA Glenn Research Center in Cleveland, OH), which is one of several rover concepts designed to excavate and transfer regolith to the stationary hydrogen reduction plants. Spaceflight versions of the MIMOS II are part of the instrument payloads of NASA s Mars Exploration Rovers and still operating five years after landing on the surface of the planet. MIMOS II was also selected for Phobos-Grunt, a Russian sample return mission to the martian moon Phobos scheduled to launch in 2009, and ESA s ExoMars rover, an exobiology mission scheduled to launch in 2013. An advanced version of the instrument is currently under development. A new detector system with a higher energy resolution will not only reduce the necessary measurement time considerably, but also allow the simultaneous acquisition of an X-ray fluorescence spectrum to determine the elemental composition of samples.

  14. Comparison of Synchrotron MicroXANES Determination of Fe(3+)/Sigma Fe with Moessbauer Values for Clean Mineral Separates of Pyroxene from Martian Meteorites

    NASA Technical Reports Server (NTRS)

    Delaney, J. S.; Dyar, M. D.

    2003-01-01

    The oxidation state of Fe in Martian meteorites is a parameter of great interest and the ability to determine this value in micrometer scale samples is important. Intense, tunable x-ray sources at large synchrotron storage rings are being exploited to examine the Fe K-absorption edge with energy resolution of approx. 1-1.5eV in spots of 10x15 microns on thin sections of a wide variety of materials including several Martian meteorites. Synchrotron microXANES (SmX) spectroscopy is the technique that provides the most flexible capability for investigating Fe(3+)/Sigma Fe. Variation of Fe(3+)/Sigma Fe is manifested as a function of the energy of the pre-edge to the Fe absorption edge produced by the sample. SmX is at present the only technique that can be used with conventional polished thin sections. Data for a broad spectrum of minerals have been produced and indicate that SmX can be used with a large variety of samples types.

  15. In Situ Resource Utilization (ISRU) on the Moon: Moessbauer Spectroscopy as a Process Monitor for Oxygen Production. Results from a Field Test on Mauna Kea Volcano, Hawaii

    NASA Technical Reports Server (NTRS)

    Morris, R.V.; Schroder, C.; Graff, T.G.; Sanders, G.B.; Lee, K.A.; Simon, T.M.; Larson, W.E.; Quinn, J.W.; Clark, L.D.; Caruso, J.J.

    2009-01-01

    Essential consumables like oxygen must to be produced from materials on the lunar surface to enable a sustained, long-term presence of humans on the Moon. The Outpost Precursor for ISRU and Modular Architecture (OPTIMA) field test on Mauna Kea, Hawaii, facilitated by the Pacific International Space Center for Exploration Systems (PISCES) of the University of Hawaii at Hilo, was designed to test the implementation of three hardware concepts to extract oxygen from the lunar regolith: Precursor ISRU Lunar Oxygen Testbed (PILOT) developed by Lockheed Martin in Littleton, CO; Regolith & Environmental Science and Oxygen & Lunar Volatiles Extraction (RESOLVE) developed at the NASA Kennedy Space Center in Cape Canaveral, FL; and ROxygen developed at the NASA Johnson Space Center in Houston, TX. The three concepts differ in design, but all rely on the same general principle: hydrogen reduction of metal cations (primarily Fe2+) bonded to oxygen to metal (e.g., Fe0) with the production of water. The hydrogen source is residual hydrogen in the fuel tanks of lunar landers. Electrolysis of the water produces oxygen and hydrogen (which is recycled). We used the miniaturized M ssbauer spectrometer MIMOS II to quantify the yield of this process on the basis of the quantity of Fe0 produced. Iron M ssbauer spectroscopy identifies iron-bearing phases, determines iron oxidation states, and quantifies the distribution of iron between mineral phases and oxidation states. The oxygen yield can be calculated by quantitative measurements of the distribution of Fe among oxidation states in the regolith before and after hydrogen reduction. A M ssbauer spectrometer can also be used as a prospecting tool to select the optimum feedstock for the oxygen production plants (e.g., high total Fe content and easily reduced phases). As a demonstration, a MIMOS II backscatter spectrometer (SPESI, Germany) was mounted on the Cratos rover (NASA Glenn Research Center in Cleveland, OH), which is one of several rover concepts designed to excavate and transfer regolith to the stationary hydrogen reduction plants. Spaceflight versions of the MIMOS II are part of the instrument payloads of NASA s Mars Exploration Rovers and still operating five years after landing on the surface of the planet. MIMOS II was also selected for Phobos-Grunt, a Russian sample return mission to the martian moon Phobos scheduled to launch in 2009, and ESA s ExoMars rover, an exobiology mission scheduled to launch in 2013. An advanced version of the instrument is currently under development. A new detector system with a higher energy resolution will not only reduce the necessary measurement time considerably, but also allow the simultaneous acquisition of an X-ray fluorescence spectrum to determine the elemental composition of samples.

  16. Magnetic studies of Sn0.2Cr1.8-xFexO3 compounds prepared via the hydrothermal route

    NASA Astrophysics Data System (ADS)

    Mbela, Kalengay; Moyo, T.; Msomi, J. Z.

    2015-07-01

    Tin-iron chromium oxides (Sn0.2Cr1.8-xFexO3 with x varying from 0.3 to 1.3) have been produced by hydrothermal process in a stirred pressure reactor from pure metal chlorides. Single phase corundum structure and nanophase structure of the as-synthesized samples were confirmed by X-ray diffraction (XRD) and by transmission electron microscope (TEM). The results show that the produced powders have grain sizes in the range 25-34 nm. 57Fe Mössbauer spectra show the materials to be paramagnetic for Fe concentration x≤0.5 and in ordered magnetic state at higher concentration. The variations of grain sizes, lattice parameters, and Mössbauer parameters as a function of composition have also been investigated. The coercivity increases rapidly with size, attaining a maximum value, and then decreases with size of the particles.

  17. Mössbauer study of the magnetic phase composition of single-crystalline rutile (TiO2) implanted with iron ions

    NASA Astrophysics Data System (ADS)

    Dulov, E. N.; Ivoilov, N. G.; Khripunov, D. M.; Tagirov, L. R.; Khaibullin, R. I.; Valeev, V. F.; Nuzhdin, V. I.

    2009-06-01

    Depth-resolved Mössbauer measurements have been performed for four ferromagnetic samples obtained by the implantation of iron ions (enriched to ˜ 50% with 57Fe isotope) into single-crystalline rutile (TiO2) substrates with two crystallographic orientations [(100) and (001)] at different temperatures (300 and 900 K). It is established that the ferromagnetic properties of iron-implanted rutile samples at room temperature are determined by the presence of α-Fe and Fe3O4 phases. The phase composition of samples obtained by iron implantation into substrates heated to 900 K depends on the crystallographic orientation of the substrate, which is explained by a significant anisotropy of the diffusion of iron atoms in rutile.

  18. Antimony and silicon environments in antimony silicate glasses

    SciTech Connect

    Mee, M.; Davies, B.C.; Orman, R.G.; Thomas, M.F.; Holland, D.

    2010-09-15

    Antimony silicate glasses, of general formula xSb{sub 2}O{sub 3}.(1-x)SiO{sub 2} (0.1{<=}x{<=}0.78), have been prepared by melt-quenching and their structures studied using {sup 29}Si MAS NMR spectroscopy, {sup 121}Sb Moessbauer spectroscopy and Raman spectroscopy. Oxidation during melting gives rise to Sb{sup 5+} in concentrations, which increase linearly with x to give a value of {approx}10% when x=0.78. {sup 121}Sb Moessbauer spectra show Moessbauer shifts and quadrupole splittings consistent with Sb{sup 3+} in a [:SbO{sub 3}] trigonal pyramid, similar to that in crystalline Sb{sub 2}O{sub 3}. A broad band in the Raman spectrum at {approx}410 cm{sup -1} is due to the vibrations of such a unit. The dependence of the silicon Q{sup n} speciation on x can be interpreted by the formation of Sb-O-Sb links possibly to form rings of 4 [:SbO{sub 3}] units such as are found in valentinite. - Graphical abstract: Antimony silicate glasses have been shown to contain Sb{sup 3+} in [:SbO{sub 3}] trigonal pyramid units using {sup 121}Sb Moessbauer spectroscopy and Raman spectroscopy. {sup 29}Si magic-angle-spinning NMR has shown silicon Q{sup n} speciation which can be interpreted as formation of rings of 4 [:SbO{sub 3}] units such as are found in valentinite.

  19. The Microscopic Magnetic Properties of W-type Hexaferrite Powder Prepared by A Sol-Gel Route

    SciTech Connect

    Jotania, Rajshree; Chauhan, Chetna; Sharma, Pooja

    2010-12-01

    Magnetic particles of W-type barium-calcium hexaferrite (BaCa{sub 2}Fe{sub 16}O{sub 27}) have been synthesized using a Stearic acid gel route. The gel precursors were dried at 100 deg. C for 2 hrs and then calcinated at 650 deg. C, 750 deg. C, 850 deg. C and 950 deg. C for 4 hrs in a furnace and slowly cooled to room temperature in order to obtain barium-calcium hexaferrite particles. The microscopic magnetic properties of prepared samples studying using Moessbauer spectroscopy. Moessbauer spectra of all samples were recorded at room temperature. Mossbauer parameters like Isomer shift, Quadruple splitting etc. were calculated with respect to iron foil. Barium calcium hexaferrite samples heated at 650 deg. C, 750 deg. C, 850 deg. C show relaxation type Moessbauer spectra along with paramagnetic doublet. The intensity of paramagnetic doublet increases with temperature confirm the presence of ferrous ions in the samples, where as sample calcinated at 950 deg. C confirm the presence of ferrimagnetic phase with partial super paramagnetic nature of prepared hexaferrite sample.

  20. Who Studies Women's Studies?

    ERIC Educational Resources Information Center

    Price, Marion; Owen, Mairead

    1998-01-01

    Studied a cohort (originally 44) of students who entered a British university to study women's studies in 1994. The strong emphases on the salience of the students' choice and the experiential importance of identity as a concept were striking. Theoretical difficulties in theorizing identity are explored. (SLD)

  1. Mössbauer study of metallic iron and iron oxide nanoparticles having environmental purifying ability

    SciTech Connect

    Kubuki, Shiro Watanabe, Yuka Akiyama, Kazuhiko; Ristić, Mira; Krehula, Stjepko; Homonnay, Zoltán; Kuzmann, Ernő; Nishida, Tetsuaki

    2014-10-27

    A relationship between local structure and methylene blue (MB) decomposing ability of nanoparticles (NPs) of metallic iron (Fe{sup 0}) and maghemite (γ‐Fe{sub 2}O{sub 3}) was investigated by {sup 57}Fe Mössbauer spectroscopy, X-ray diffractometry and UV-visible light absorption spectroscopy. γ‐Fe{sub 2}O{sub 3} NPs were successfully prepared by mixing (NH{sub 4}){sub 2}Fe(SO{sub 4}){sub 2}⋅6H{sub 2}O (Mohr's salt) and (NH{sub 4}){sub 3}Fe(C{sub 2}O{sub 4}){sub 3}⋅3H{sub 2}O aqueous solution at 30 °C for 1 h, while those of Fe{sup 0} were obtained by the reduction of Mohr's salt with NaBH{sub 4}. From the Scherrer's equation, the smallest crystallite sizes of γ‐Fe{sub 2}O{sub 3} NPs and Fe{sup 0} NPs were determined to be 9.7 and 1.5 nm, respectively. {sup 57}Fe Mössbauer spectrum of γ‐Fe{sub 2}O{sub 3} NPs consists of a relaxed sextet with isomer shift (δ) of 0.33{sub ±0.01} mm s{sup −1}, internal magnetic field (H{sub int}) of 25.8{sub ±0.5} T, and linewidth (Γ) of 0.62{sub ±0.04} mm s{sup −1}. {sup 57}Fe Mössbauer spectrum of Fe{sup 0} NP is mainly composed of a sextet having δ, Δ, and H{sub int} of 0.00{sub ±0.01} mm s{sup −1} 0.45{sub ±0.01} mm s{sup −1}, and 22.8{sub ±0.1} T, respectively. A bleaching test of the mixture of Fe{sup 0} and γ‐Fe{sub 2}O{sub 3} NPs (3:7 ratio, 100 mg) in MB aqueous solution (20 mL) for 6 h showed a remarkable decrease of MB concentration with the first-order rate constant (k{sub MB}) of 6.7 × 10{sup −1} h{sup −1}. This value is larger than that obtained for the bleaching test using bulk Fe{sup 0}+γ‐Fe{sub 2}O{sub 3} (3:7) mixture (k{sub MB} = 6.5×10{sup −3}h{sup −1}). These results prove that MB decomposing ability is enhanced by the NPs mixture of Fe{sub 0} and γ‐Fe{sub 2}O{sub 3}.

  2. An investigation of the mechanism of detoxification in asbestos

    NASA Astrophysics Data System (ADS)

    Hearne, G. R.; Pollak, H.; van Wyk, J. A.; Gulumian, M.

    1992-10-01

    57Fe Mössbauer effect spectroscopy studies were conducted on native crocidolite and on a sample which had been detoxified by means of a chemical treatment with ferric salts. This allows for a comparison between the crystal chemistry of the untreated and treated samples. Significant chemical changes in the treated sample have been inferred from the Fe site-population analysis after conducting a temperature-dependent study of both samples in the range 300 K down to 90 K. These results, together with the results from complementary Electron Spin Resonance (ESR) studies, may help to elucidate the mechanism of toxicity in these asbetiforms.

  3. Mössbauer study of new vanadate glass with large charge-discharge capacity

    NASA Astrophysics Data System (ADS)

    Kubuki, Shiro; Masuda, Hitomi; Matsuda, Koken; Akiyama, Kazuhiko; Kitajo, Ayuko; Okada, Shigeto; Zsabka, Péter; Homonnay, Zoltán; Kuzmann, Ernõ; Nishida, Tetsuaki

    2014-04-01

    Charge-discharge capacity and cyclicity of lithium ion battery (LIB) was evaluated in which 15Li2O·10Fe2O3· xSnO2·5P2O5·(70- x)V2O5 glass ( x = 0 and 20 in mol%, abbreviated as xLFSPV) was used as a cathode. A local structure of xLFSPV glass before and after charging was investigated by 57Fe- and 119Sn-Mössbauer spectroscopies. 57Fe-Mössbauer spectrum of xLFSPV glass with ` x' of 20 was composed of a doublet with isomer shift ( δ) of 0.35±0.02 mm s - 1 and quadrupole splitting ( Δ) of 0.88±0.03 mm s - 1 due to distorted FeIIIO4 tetrahedra. 119Sn-Mössbauer spectrum of this glass consisted of a doublet with δ of 0.08±0.01 and Δ of 0.52±0.01 mms - 1 due to distorted SnVIO6 octahedra. After discharging the battery from 4.5 to 1.0 V, larger δ of 0.40±0.03 mm s - 1 and Δ of 0.94±0.04 mm s - 1 were obtained, indicating that both iconicity of Fe-O bonds and local distortion of FeIIIO4 tetrahedra were increased. On the contrary, identical δ of 0.09±0.01 mm s - 1 and Δ of 0.50±0.01 mm s - 1 were observed in the 119Sn-Mössbauer spectrum of 20LFSPV glass after the discharge, indicating that chemical environment of SnIVO6 octahedra was not affected after the discharge. Charge-discharge curve of LIB containing 20LFSPV glass as a cathode active material recorded under the current density of 8.3 mA g - 1 (0.011 mA cm - 2) between 1.0 and 4.5 V showed a large initial charge capacity of 431.1 mAh g - 1 and discharge capacity of 382.3 mAh g - 1, respectively. These results indicate that 20LFSPV glass could be a new cathode active material for LIB.

  4. The Electronic Structure of Metallic and Bimetallic Clusters of IRON-57 with Chromium, TIN-119 and Platinum.

    NASA Astrophysics Data System (ADS)

    Nagarathna, H. M.

    Rare gas matrix isolation techniques have been used in conjunction with Mossbauer spectroscopy to study the bimetallic clusters of ('57)Fe with Cr, ('119)Sn and Pt. Various molecules have been identified by concentration and temperature dependence studies and also with the aid of Monte Carlo calculations. The iron-tin system is studied using both ('57)Fe and ('119)Sn Mossbauer isotopes. The Mossbauer parameters of FeCr, FeSn and FePt heteronuclear diatomic molecules and Sn(,2) homonuclear diatomic molecules isolated in argon at 4.2 K are obtained very accurately and used to determine their electronic ground states. In addition to diatomic molecules, the larger clusters have also been characterized using Mossbauer spectroscopy and their relevance to bulk alloys is discussed. SCF-X(alpha)-SW molecular orbital calculations are performed on Fe(,2), FeCr, Sn(,2), FeSn and FePt diatomic molecules to determine their electronic ground states by looking at the calculations which agreed with the measured Mossbauer hyperfine parameters. The most probable electronic ground state for Fe(,2) is determined to be a ('7)(SIGMA)(,g) and for FeCr a ('7)(SIGMA) or ('7)(DELTA) indicating a ferromagnetic coupling between the atoms. The calculations indicated a need for a smaller value of the quadrupole moment of the ('57)Fe nucleus. For Sn(,2) a ('3)(SIGMA)(,g) is the most probable ground state and for FeSn a ('7)(DELTA). The calculations showed a ('5)(SIGMA) state as the most probable electronic ground state for FePt. The X(alpha)-SW calculations are found to be very useful in understanding the nature of chemical bonding between the atoms in the above molecules. Antimony metal clusters are also studied using ('121)Sb Mossbauer spectroscopy and extended Huckel molecular orbital calculations. A good correlation is observed between the experimental and calculated data.

  5. Comparative study of the iron cores in human liver ferritin, its pharmaceutical models and ferritin in chicken liver and spleen tissues using Mössbauer spectroscopy with a high velocity resolution.

    PubMed

    Alenkina, I V; Oshtrakh, M I; Klepova, Yu V; Dubiel, S M; Sadovnikov, N V; Semionkin, V A

    2013-01-01

    Application of Mössbauer spectroscopy with a high velocity resolution (4096 channels) for comparative analysis of iron cores in a human liver ferritin and its pharmaceutically important models Imferon, Maltofer(®) and Ferrum Lek as well as in iron storage proteins in chicken liver and spleen tissues allowed to reveal small variations in the (57)Fe hyperfine parameters related to differences in the iron core structure. Moreover, it was shown that the best fit of Mössbauer spectra of these samples required different number of components. The latter may indicate that the real iron core structure is more complex than that following from a simple core-shell model. The effect of different living conditions and age on the iron core in chicken liver was also considered.

  6. Crystal structure and Mössbauer studies of the isotypic Fe{sub 6}-cluster compounds RE{sub 15}[Fe{sub 8}C{sub 25}], RE=Dy, Ho

    SciTech Connect

    Davaasuren, Bambar; Dashjav, Enkhtsetseg; Kreiner, Guido; Borrmann, Horst; Weber, Sven-Ulf; Becker, Klaus-Dieter; Jochen Litterst, Fred; Kniep, Rüdiger

    2015-05-15

    The carboferrates RE{sub 15}[Fe{sub 8}C{sub 25}] (RE=Dy, Ho) were prepared from mixtures of the elements by arc-melting followed with subsequent annealing at 1373 K. The crystal structures were determined from single crystal X-ray diffraction data and revealed an isotypic relationship to Er{sub 15}[Fe{sub 8}C{sub 25}] (hP48, P321). The main feature of the crystal structure is given by Fe{sub 6} cluster units characterized by covalent Fe–Fe bonding interactions. {sup 57}Fe Mössbauer spectra of Dy{sub 15}[Fe{sub 8}C{sub 25}] were fitted by three subspectra with relative spectral weights of about 3:3:2 which is in general agreement with the crystal structure. Below 50 K, an onset of magnetic hyperfine fields at the three iron sites is observed which is supposed to be caused by dipolar fields arising from neighboring, slowly relaxing Dy magnetic moments. - Graphical abstract: Fe{sub 6}-cluster in the crystal structure of RE{sub 15}[Fe{sub 8}C{sub 25}], RE=Dy, Ho. - Highlights: • New carboferrates RE{sub 15}[Fe{sub 8}C{sub 25}] with RE=Dy, Ho have been synthesized. • The crystal structures were refined using single crystal X-ray data. • An orientational relationship between Fe{sub 6}-clusters and Fe in γ-Fe is outlined. • {sup 57}Fe Mössbauer spectra are in agreement with structural data from X-rays. • Magnetic hyperfine fields below 50 K are explained by dipolar fields from Dy atoms.

  7. A Study of the Magnetic and Thermal Properties of Ln

    SciTech Connect

    Harada, Daijitsu; Hinatsu, Yukio

    2001-05-01

    Crystal structures, and magnetic, electric, and thermal properties of fluorite related compounds Ln{sub 3}RuO{sub 7} (Ln=Sm, Eu) have been investigated. For Eu{sub 3}RuO{sub 7}, a magnetic transition due to Ru{sup 5+} ions is found at T{sub N}=22.5 K on the susceptibility-temperature curve. Specific heat measurements also exhibit a {lambda}-type anomaly at the same temperature. The Moessbauer spectrum measured at 10 K shows broadening of the line corresponding to magnetic splitting. For Sm{sub 3}RuO{sub 7}, two magnetic anomalies have been observed at 10.5 and 22.5 K from its magnetic susceptibility measurements. Below 22.5 K Ru{sup 5+} ions are antiferromagnetically coupled, and when the temperature is decreased through 10.5 K the ordering of Sm{sup 3+} ions occurs rapidly. Specific heat measurements show first-order transition peaks at T=280 and 190 K for Eu{sub 3}RuO{sub 7} and Sm{sub 3}RuO{sub 7}, respectively. T he results of magnetic susceptibility and electric resistivity measurements indicate that these transitions are structural phase transitions.

  8. Consortium study of the unusual H chondrite regolith breccia, Noblesville

    NASA Technical Reports Server (NTRS)

    Lipschutz, Michael E.; Wolf, Stephen F.; Vogt, Stephan; Michlovich, Edward; Lindstrom, Marilyn M.; Zolensky, Michael E.; Mittlefehldt, David W.; Satterwhite, Cecilia; Schultz, Ludolf; Loeken, Thomas

    1993-01-01

    The Noblesville meteorite is a genomict, regolith breccia (H6 clasts in H4 matrix). Moessbauer analysis confirms that Noblesville is unusually fresh, not surprising in view of its recovery immediately after its fall. It resembles 'normal' H4-6 chondrites in its chemical composition and induced thermoluminescence (TL) levels. Thus, at least in its contents of volatile trace elements, Noblesville differs from other H chondrite, class A regolith breccias. Noblesville's small pre-atmospheric mass and fall near solar maximum and/or its peculiar orbit (with perihelion less than 0.8 AU as shown by natural TL intensity) may partly explain its levels of cosmogenic radionuclides. Its cosmic ray exposure age of about 44 Ma is long, is equalled or exceeded by less than 3 percent of all H chondrites, and also differs from the 33 +/- 3 Ma mean exposure age peak of other H chondrite regolith breccias. While Noblesville is now among the chondritic regolithic breccias richest in solar gases, elemental ratios indicate some loss, especially of He, perhaps by impacts in the regolith that heated individual grains. While general shock-loading levels in Noblesville did not exceed 4 GPa, individual clasts record shock levels of 5-10 GPa, doubtless acquired prior to lithification of the whole-rock meteoroid.

  9. Consortium study of the unusual H chondrite regolith breccia, Noblesville

    NASA Technical Reports Server (NTRS)

    Lipschutz, Michael E.; Wolf, Stephen F.; Vogt, Stephan; Michlovich, Edward; Lindstrom, Marilyn M.; Zolensky, Michael E.; Mittlefehldt, David W.; Satterwhite, Cecilia; Schultz, Ludolf; Loeken, Thomas

    1993-01-01

    The Noblesville meteorite is a genomict, regolith breccia (H6 clasts in H4 matrix). Moessbauer analysis confirms that Noblesville is unusually fresh, not surprising in view of its recovery immediately after its fall. It resembles 'normal' H4-6 chondrites in its chemical composition and induced thermoluminescence (TL) levels. Thus, at least in its contents of volatile trace elements, Noblesville differs from other H chondrite, class A regolith breccias. Noblesville's small pre-atmospheric mass and fall near solar maximum and/or its peculiar orbit (with perihelion less than 0.8 AU as shown by natural TL intensity) may partly explain its levels of cosmogenic radionuclides. Its cosmic ray exposure age of about 44 Ma is long, is equalled or exceeded by less than 3 percent of all H chondrites, and also differs from the 33 +/- 3 Ma mean exposure age peak of other H chondrite regolith breccias. While Noblesville is now among the chondritic regolithic breccias richest in solar gases, elemental ratios indicate some loss, especially of He, perhaps by impacts in the regolith that heated individual grains. While general shock-loading levels in Noblesville did not exceed 4 GPa, individual clasts record shock levels of 5-10 GPa, doubtless acquired prior to lithification of the whole-rock meteoroid.

  10. Iron Isotope Fractionation in the Lower Mantle

    NASA Astrophysics Data System (ADS)

    Yang, H.; Lin, J. F.; Dauphas, N.

    2015-12-01

    Knowledge of iron isotopes in the deep Earth is of great importance, for it provides clues for determining the history of planetary differentiation and core formation, as well as the origin of the Earth. However, iron isotope composition of the Earth's interior is rarely known due to lack of samples. Previous theoretical and experimental results are insufficient because they presume the spin state of iron or they are based on relatively low quality experimental data. Here we will use a newly developed technique --NRIXS(Nuclear Resonant Inelastic X-ray Scattering)-- to measure the force constant of lower mantle mineral candidates ferropericlase and pervoskite at relevant pressure. A reliable iron isotope fractionation factor will then be derived using SciPhon, which is a software designed specifically for the isotope fractionation factor derivation from NRIXS data. We report new high pressure 57Fe NRIXS spectra collected at beamline 3 ID-B of the Advanced Photon Source, with the aim to understand the pressure effect on iron isotope fractionation. The experiments were conducted using a 3-fold Diamond Anvil Cell and a >95% 57Fe enriched sample fp25((Fe0.25Mg0.75)O). NRIXS spectra were collected by tuning the x-ray energy range within ± 200meV around the 57Fe resonant energy of 14.4125keV. We will present the force constants and derived iron isotope fractionation factors of ferropericlase. It is expected that pressure will have an effect on the iron isotope fractionation factor and should be taken into account when modeling isotope fractionation of planetary scale and when using iron isotope systems to constrain the planetary differentiation. We will also use first-principle studies and geochemical observations to study the Fe,O,Si isotope system in the deep Earth. Our ultimate goal is to build a self-consistent geophysical and geochemical model that can be used in deciphering the mystery of Earth's history.

  11. Effect of biaxial strain on the phase transitions of Ca(Fe1–xCox)2As2

    DOE PAGES

    Bohmer, A. E.; Sapkota, A.; Kreyssig, A.; ...

    2017-03-10

    We study the effect of applied strain as a physical control parameter for the phase transitions of Ca(Fe1–xCox)2As2 using resistivity, magnetization, x-ray diffraction, and 57Fe Mossbauer spectroscopy. Biaxial strain, namely, compression of the basal plane of the tetragonal unit cell, is created through firm bonding of samples to a rigid substrate via differential thermal expansion. This strain is shown to induce a magnetostructural phase transition in originally paramagnetic samples, and superconductivity in previously nonsuperconducting ones. Lastly, the magnetostructural transition is gradual as a consequence of using strain instead of pressure or stress as a tuning parameter.

  12. Distribution of electric and magnetic hyperfine fields in Fe-rich gallo-germanates

    NASA Astrophysics Data System (ADS)

    Constantinescu, S.

    The crystal field disorder in some tetragonal and trigonal Ca-gallo-germanates, i.e., A2Fe2Z07 and A2LnFe3Ge3014 with A=Ba or Sr, Ln=La or Nd and Z=Ge or Si, has been studied by 57Fe Mössbauer spectroscopy. The observed distribution of the hyperfine fields is analysed from a theoretical model based on the additive perturbation approximation of crystal fields, a rigid lattice of ionic point charges and the random substitution of Fe3+/Z4+ and A2+/Ln3+.

  13. Distribution of electric and magnetic hyperfine fields in Fe-rich gallo-germanates

    NASA Astrophysics Data System (ADS)

    Constantinescu, S.

    2006-02-01

    The crystal field disorder in some tetragonal and trigonal Ca-gallo-germanates, i.e., A2Fe2ZO7 and A2LnFe3Ge3O14, with A = Ba or Sr, Ln = La or Nd and Z = Ge or Si, has been studied by 57Fe Mössbauer spectroscopy. The observed distribution of the hyperfine fields is analysed from a theoretical model based on the additive perturbation approximation of crystal fields, a rigid lattice of ionic point charges and the random substitution of Fe3+/Z4+ and A2+/Ln3+.

  14. Phase separation in lanthanum manganites

    NASA Astrophysics Data System (ADS)

    Sedykh, Vera D.

    2016-10-01

    The structural transformations in doped lanthanum manganites La1-xMexMnO3+δ (Me = Ca, Sr, Ba) (with a small amount of 57Fe (2%) for Mössbauer experiments) have been studied in a wide concentration range of a doping element (0 < x < 0.2) by Mössbauer spectroscopy and X-ray diffraction analysis. A mixture of three orthorhombic phases has been shown to be formed in all these compounds of a stoichiometric composition, i.e., a structural phase separation takes place. The phase relations for different doping element types and contents significantly differ. The reasons of phase separation in lanthanum manganites are discussed.

  15. Generation of superparamagnetism in metallic α-iron by swift heavy ion irradiation

    NASA Astrophysics Data System (ADS)

    Kuzmann, E.; Stichleutner, S.; Homonnay, Z.; Havancsák, K.; Chisholm, C. U.; El-Sharif, M.; Skuratov, V. A.; Nakanishi, A.; Nomura, K.

    2016-10-01

    57Fe conversion electron Mössbauer spectroscopy was used to study the effect of swift heavy ion irradiation on electrochemically deposited metallic pure α-iron. We succeeded in preparing superparamagnetic iron by irradiating the electrochemically prepared thin α-iron films using 247 MeV Kr ions with a fluence of 1×1013 ion cm-2 which converted 50% of crystalline α-iron into amorphous and superparamagnetic phases, the latter being >20%. The results are discussed in terms of the thermal spike model for the formation of the amorphous phase which could be essential for the formation of superparamagnetic iron.

  16. Nuclear forward scattering of synchrotron radiation in pulsed high magnetic fields.

    PubMed

    Strohm, C; Van der Linden, P; Rüffer, R

    2010-02-26

    We report the demonstration of nuclear forward scattering of synchrotron radiation from 57Fe in ferromagnetic alpha iron in pulsed high magnetic fields up to 30 T. The observed magnetic hyperfine field follows the calculated high field bulk magnetization within 1%, establishing the technique as a precise tool for the study of magnetic solids in very high magnetic fields. To perform these experiments in pulsed fields, we have developed a detection scheme for fully time resolved nuclear forward scattering applicable to other pump probe experiments.

  17. Influence of magnetic annealing and interdiffusion on the exchange bias of CoFe/IrMn

    NASA Astrophysics Data System (ADS)

    Macedo, Waldemar; Fernandez-Outon, Luis; Araujo Filho, Mario; Araujo, Raphael; Ardisson, Jose

    2013-03-01

    Magnetic annealing is broadly used to set exchange bias (EB). The EB field depends on the magnetic field and the temperature at which the F/AF exchange interaction is set. Atomic interdiffusion is also expected to have strong influence on EB. For systems containing IrMn, different results have been reported regarding the effect of setting EB between 200 and 400 °C. We study the effect of atomic interdiffusion on the exchange bias of polycrystalline IrMn/(57Fe +CoFe) multilayers due to the magnetic annealing between 225 and 500 °C. The samples have been prepared by magnetron sputtering, and 57Fe probe layers (10 Å thick) were grown at the F/AF interface, and 1 nm and 2 nm above it, inside the CoFe layer. Depth-resolved 57Fe conversion electron Mössbauer spectroscopy (CEMS) was used to quantify atomic interdiffusion, and vibrating sample magnetometry was used to monitor the variation of exchange bias and magnetisation. We found that interface sharpness is only affected above ~350 °C. Three different stages for the setting of exchange bias can be inferred from our results. At temperatures < 350 °C, no interdiffusion is observed and the F/AF exchange coupling establishes partial spin alignment of interfacial and bulk AF spins. At intermediate setting temperatures (350-450 °C) interfacial spin order is dominant over chemical intermixing effects, and both exchange field and coercivity increase up to 450 °C. Above 450 °C, severe chemical intermixing reduces significantly (~50%) the F/AF coupling. Work supported by CAPES/PNPD, FAPEMIG, and CNPq

  18. Hyperfine interactions in nanocrystallized NANOPERM-type metallic glass containing Mo

    NASA Astrophysics Data System (ADS)

    Cesnek, M.; Kubániová, D.; Kohout, J.; Křišťan, P.; Štěpánková, H.; Závěta, K.; Lančok, A.; Štefánik, M.; Miglierini, M.

    2016-12-01

    NANOPERM-type alloy with chemical composition Fe76Mo8CuB15 was studied by combination of 57Fe Mössbauer spectroscopy and 57Fe(10B, 11B) nuclear magnetic resonance in order to determine distribution of hyperfine magnetic fields and evolution of relative concentration of Fe-containing crystalline phases within the surface layer and the volume of the nanocrystallized ribbons with annealing temperature. Differential scanning calorimetry revealed two crystallization stages at T x1 ˜ 510 ∘C and T x2 ˜ 640 ∘C, connected to precipitation of α-Fe and Fe(Mo,B) nanocrystals, respectively. The amorphous and partially crystalline state was obtained by annealing at several temperatures in the range 510-650 ∘C. The combination of conversion electron (CEMS) and transmission Mössbauer spectrometry (TMS) showed that annealing induces crystallization starting from both surfaces of the ribbons. For the as-quenched sample, scanning electron microscopy (SEM) and CEMS revealed significant differences in the "air" and "wheel" sides of the ribbons, crystallites were preferentially formed at the latter. While SEM micrographs of annealed samples showed various mean diameters of the crystals at opposite sides of the ribbons, the amounts of crystalline volume derived from the CEMS spectra approximately equaled. Mössbauer spectra of annealed samples contained narrow sextet ascribed to crystalline α-Fe phase, three sextets with distribution of hyperfine field assigned to the interface regions of the nanocrystals and the contribution of the amorphous phases. In-field TMS performed at 4.2 K with magnetic moments aligned by external magnetic field enabled to properly determine in particular the contribution of the amorphous phases in the samples. Resulting distributions of the hyperfine fields were compared with 57Fe(10B, 11B) nuclear magnetic resonance (NMR) spectra.

  19. Iron Absorption from an Intrinsically Labeled Lentil Meal Is Low but Upregulated in Women with Poor Iron Status.

    PubMed

    DellaValle, Diane M; Glahn, Raymond P; Shaff, Jon E; O'Brien, Kimberly O

    2015-10-01

    Low iron absorption from important staple foods may contribute to iron deficiency in developing countries. To date, few studies have examined the iron bioavailability of pulse crops as commonly prepared and consumed by humans. The objectives were to characterize the iron absorption from a test meal of intrinsically labeled (57)Fe lentils prepared as dal, to compare the bioavailability of iron from (57)Fe in dal with that observed for a reference dose of (58)Fe as ferrous sulfate, and to assess associations between iron absorption and iron status indicators. This crossover study included 19 nonpregnant women (n = 6 anemic; hemoglobin: <12.0 g/dL) who consumed 2 test meals on consecutive days in a counter-balanced order, ferrous sulfate (7 mg FeSO4 plus 1 mg (58)Fe) and 330 g dal (lentils enriched to 85.1% with (57)Fe, 8 mg native (57)Fe). Iron absorption was determined by analyzing blood samples taken 14 d after dosing with the use of magnetic sector thermal ionization mass spectrometry. We found that the mean iron absorption from the dal was 2.20% ± 3.40% and was significantly lower than the 23.6% ± 13.2% observed from the same iron load given as ferrous sulfate (P < 0.001). Absorption of non-heme iron from dal and from ferrous sulfate was inversely associated with serum ferritin (SF; r = -0.50, P = 0.05 and r = -0.81, P < 0.001, respectively) and serum hepcidin (r = -0.45, P = 0.05 and r = -0.60, P = 0.007, respectively). Anemic women absorbed more iron from either source (1.20% from dal, P = 0.10; 18.3% from ferrous sulfate, P = 0.001) compared with women who were iron replete. Iron absorption from the dal was low overall but upregulated in anemic women. Both SF and hepcidin were inversely associated with iron absorption from both a supplemental and a food-based non-heme iron source in nonanemic and anemic women. © 2015 American Society for Nutrition.

  20. Spectroscopic studies on the interaction of phosphate with uteroferrin.

    PubMed

    Doi, K; Gupta, R; Aisen, P

    1987-05-25

    The effect of phosphate on the binuclear iron center of pink (reduced) uteroferrin was examined by magnetic resonance and optical spectroscopy. The purple (oxidized) protein, which contains 1 mol of tightly bound phosphate per mol of enzyme at isolation, does not give rise to a 31P NMR signal. Phosphate binding to phosphate-stripped pink uteroferrin is indistinguishable from that in the native purple phosphoprotein. As measured by EPR and optical spectroscopy, the rate of reaction between phosphate and pink uteroferrin is pH-dependent, decreasing as the pH increases. Phosphate is capable of binding to the reduced protein between pH 3 and 7.8, resulting in formation of the purple uteroferrin-phosphate complex. Evans susceptibility measurements at pH 4.9 indicate that the EPR silent species with a maximum absorption at 535 nm, generated upon phosphate addition to pink uteroferrin, is diamagnetic. Moreover, phosphate causes disappearance of the hyperfine-shifted resonances in the 1H NMR spectra of the reduced protein. We therefore have not been able to identify the paramagnetic "purple reduced enzyme-phosphate complex" reported by Pyrz et al. (Pyrz, J. W., Sage, J. T., Debrunner, P. G., and Que, Jr., L. (1986) J. Biol Chem. 261, 11015-11020) using Mossbauer spectroscopy and dithionite-reduced 57Fe-reconstituted uteroferrin. Our present data with native unmodified enzyme are in accord with our earlier results (Antanaitis, B. C., and Aisen, P. (1985) J. Biol. Chem. 260, 751-756) and with the results of Burman et al. (Burman, S., Davis, J. C., Weber, M. J., and Averill, B. A. (1986) Biochem. Biophys. Res. Commun. 136, 490-497) on bovine spleen phosphatase, suggesting that phosphate binding to reduced protein rapidly induces oxidation of the binuclear iron center.