Intracluster and Intercluster Interactions in Nanostructures

The formation and properties of three types of nanostructures: solid-state nanostructures, matrix nanostructures and nanostructures under high pressure with shear were studied. Nanocluster peculiarities: solid-liquid state and first-order (jump-wise) magnetic phase transitions were considered. The influence of cluster-cluster interactions, cluster-matrix interactions and cluster defects on cluster atomic dynamics, cluster melting, cluster critical sizes, Curie or Néel points and the character of magnetic phase transitions were investigated. This revised version was published online in August 2006 with corrections to the Cover Date.     

The Magnetism of Frustrated RFe6Al6 Compounds Studied by μSR and Mössbauer Spectroscopy

Hyperfine Interactions - μSR studies on the RFe6Al6 (R?=?Tb,?Ho,?Er) ferrimagnets (T N≈340?K) show that the presence of frustration by competing exchange...     

Energy and line width in the induced emission of Mössbauer radiation

Summary Some promising schemes proposed for extending the range of lasers to the X-ray and gamma-ray regions are those involving a transition from a long-lived nuclear excited state. While metastable states allow the creation of conditions for population inversion, they also give rise to problems due to the narrowness of the expected line width. We discuss the line width of the radiation due to gamma transitions between excited states and derive a corrected relation for the cross-section in this case. Criteria for choosing an appropriate isotope are deduced from the corrected crosssection, showing that the problems derived from the narrowness of the line width can be avoided in a transition from an isomeric state to a lower short-lived excited state in which case the line width of the radiation is totally determined by the breadth of the lower excited state.

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Riassunto Alcuni schemi promettenti proposti per estendere il campo dei laser alle regioni dei raggi X e dei raggi gamma sono quelli che coinvolgono una transizione da uno stato eccitato nucleare a vita lunga. Mentre gli stati metastabili permettono la creazione delle condizioni per l’inversione della popolazione, essi danno luogo anche ai problemi dovuti alla ristrettezza dell’ampiezza della linea attesa. Si discute l’ampiezza di linea della radiazione dovuta alle transizioni gamma tra gli stati eccitati e si deduce una relazione corretta per la sezione d’urto in questo caso. Si deducono i criteri per scegliere un isotopo appropriato dalla sezione d’urto corretta, mostrando che i problemi che derivano dalla ristrettezza dell’ampiezza di linea si possono evitare in una transizione da uno stato isomerico a uno stato eccitato piú basso a vita breve, nel qual caso l’ampiezza di linea della radiazione si determina totalmente dalla larghezza dello stato eccitato piú basso.

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Резюме Были предложены обнадеживающие схемы для расширения области лазеров в рентгеновскую и гамма-области. Эти схемы вкяючают переход из долгоживущего ядерного возбужденного состояния. Так как метастабильные состояния допускают создание условий для инверсной заселенности, то они также приводят к проблемам, обусловленным узостью ожидаемой ширины линии. Мы обсуждаем ширину линии излучения, обусловленную гамма-переходами между возбужденными состояниями и выводим соотношение для поперечного сечения в этом случае. Выводятся критерии для выбора соответствующего изотопа из полученного поперечного сечения. Показывается, что проблемы, связанные с узостью ширины линии, можно обойти в случае перехода из изомерного состояния в низшее короткоживущее возбужденное состояние, причем в этом случае ширина линии излучения полностью определяется шириной низшего возбужденного состояния.

     

Mössbauer,X-ray fluorescence and paleomagnetic studies of deep-sea sediments from the Peru Basin: two million years of sedimentation history

Summary Sediment cores with different sub-bottom depths (I: 45 cm and II: 700 cm) from the Peru Basin have been investigated. From the depth profile of the relative amount of Fe(II) a redox zone is obtained which correlates with the organic carbon flux into the sediment (core I). M?ssbauer parameters suggest that the iron in the sediments is mainly contained in clay minerals and to varying extent also in goethite. Paper presented at ICAME-95, Rimini, 10–16 September 1995.     

Iron(III) species formed during iron(II) oxidation and iron-core formation in the bacterioferritin of Escherichia coli

Summary This paper describes a preliminary investigation of the mechanisms of Fe(II) oxidation and storage of Fe(III) in the bacterioferritin ofEscherichia coli (EcBFR). Using M?ssbauer spectroscopy to examine the initial oxidation of iron by EcBFR we have confirmed that this ferritin exhibits ?ferroxidase? activity and have shown that dimeric and monomeric iron species are produced as intermediates. We compare the characteristics of ferroxidase activity in EcBFR with those of human H-chain ferritin (HuHF) and discuss the different M?ssbauer parameters of their dimeric iron with reference to the structures of their di-metal sites. In addition, we present preliminary findings suggesting that after an initial ?burst?, the rate of oxidation is greatly reduced, possibly due to blockage of the ferroxidase centre by bound iron. A new component, not found in HuHF and probably representing a small cluster of Fe(III) atoms, is reported. Paper presented at the ICAME-95, Rimini, 10–16 September 1995.     

Amorphous Fe–Mg alloy thin films: magnetic properties and atomic vibrational dynamics

Amorphous (a-) Fe _x Mg_1?x alloys are interesting materials for the investigation of non-Debye-like low-energy vibrational excitations. We have prepared a-Fe _x Mg_1?x alloy thin films (0.3 ≤ × ≤0.7) by vapour quenching. The amorphous state was confirmed by conversion electron Mössbauer spectroscopy between 4.2–300 K, and the x- and temperature-dependence of the isomer shift and hyperfine magnetic field was measured. For x= 0.6 and 0.7, magnetic ordering occurs below ~150 K. The atomic vibrational density of states, g(E), was determined by nuclear resonant inelastic scattering, providing clear evidence for the non-Debye-like low-energy vibrational excitations.     

Magnetic Phase Transitions in Nanoclusters and Nanostructures

New phenomena – the first order magnetic phase transitions were observed in nanoclusters and nanostructures. For isolated ferrihydrite nanoclusters (d ～ 1–2 nm) in porous materials, for α-,γ-Fe₂O₃ nanoclusters (d ～ 20–50 nm) and for composites of nanostructured metallic Eu with additives of α-, γ-Fe₂O₃ nanoclusters and adamantane the critical temperatures (T _C, T _N) and magnetic cluster critical sizes (R _cr) were determined by means of thermodynamic models and Mössbauer spectroscopy. The first order magnetic phase transitions (jump-like) proceed by such a way when magnetization and magnetic order disappear by jump without superparamagnetic relaxation. According to thermodynamic model predictions the cluster and interface defects were suggested to play the main role in magnetic behavior. Thus, for the defective α-, γ-Fe₂O₃ nanoclusters, at R ≤ R _cr, the presence of the first order (jump-like) magnetic phase transition was described in terms of magnetic critical size of cluster. The action of high pressure (up to 2 GPa) with shear (120–240°) was effective for defect generation and nanostructure formation. For nanosystems including iron oxide nanoclusters, adamantane and metallic europium and subjected to shear stress under high pressure loading the critical value of defect density was estimated by the study of the character of magnetic phase transition. First-to-second-order (nanostructured metallic Eu) and second-to-first-order (α-, γ-ferric oxide nanoclusters) changes of the character of magnetic phase transition were shown to accompany by the variation of critical temperatures compared to the corresponding bulk values.     

Mössbauer study of the invar Fe–Ni and Fe–Ni–C alloys in magnetic field

F.C.C. Fe–30.3%Ni and Fe–30.5%Ni–1.5%C (wt.%) alloys were studied by means of Mössbauer spectroscopy in external magnetic field B _ext?=?2.5, 5, 7 T parallel to the gamma-beam. It is shown that distribution of effective magnetic field in the alloys is broad and that carbon expands the range of B _eff. The external magnetic field increases B _eff in the Fe–Ni alloy and decreases it more evidently in the Fe–Ni–C alloy. Antiferromagnetic spin coupling along the ferromagnetic component is proposed to explain data.     

Mössbauer and XRD study of pulse plated Fe–P and Fe–Ni thin layers

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

Mössbauer and X-ray diffraction characterization of Fe60Al40 coatings prepared by thermal spraying

Microstructured (atomized) and nanostructured (milled) Fe₆₀Al₄₀ powders together with their corresponding coatings synthesized by High Velocity Oxy-fuel (HVOF) or Atmospheric Plasma Spray (APS) thermal spraying techniques have been characterized by Mössbauer Spectroscopy (MS) and X-ray Diffraction (XRD). The evolution of the microstructure and the atomic ordering degree in the powders and coatings are discussed at the light of the various processing conditions. The operational correlation between the parameters of the duplex morphology of coatings and the processing parameters is discussed.     

Subleading long-range interactions and violations of finite size scaling

We study the behavior of systems in which the interaction contains a long-range component that does not dominate the critical behavior. Such a component is exemplified by the van der Waals force between molecules in a simple liquid-vapor system. In the context of the mean spherical model with periodic boundary conditions we are able to identify, for temperatures close above T _c, finite-size contributions due to the subleading term in the interaction that are dominant in this region decaying algebraically as a function of L. This mechanism goes beyond the standard formulation of the finite-size scaling but is to be expected in real physical systems. We also discuss other ways in which critical point behavior is modified that are of relevance for analysis of Monte Carlo simulations of such systems. Received 21 November 2000 and Received in final form 28 February 2001     

Vibrational dynamics of Fe in amorphous Fe–Sc and Fe–Al alloy thin films

The atomic vibrational dynamics of ⁵⁷Fe in 800-Å thick amorphous (a-) ⁵⁷Fe_0.25Sc_0.75, a-⁵⁷Fe_0.67Sc_0.33 and a-⁵⁷Fe_0.14Al_0.86 alloy thin films has been investigated at room temperature by nuclear resonant inelastic X-ray scattering (NRIXS) of synchrotron radiation. The amorphous phase has been successfully stabilized by codeposition of Fe and Sc or Al in ultrahigh vacuum onto substrates held at –140 °C during deposition. The amorphous structure of the samples was confirmed by X-ray diffraction and conversion electron Mössbauer spectroscopy. The ⁵⁷Fe-projected partial vibrational density of states, g(E), has been obtained from the measured NRIXS vibrational excitation probability, together with thermodynamic quantities such as the probability of recoilless absorption (f-factor), the average kinetic energy per Fe atom, the average force constant, and the vibrational entropy per Fe atom. A plot of the reduced density of states, g(E)/E², versus excitation energy E proves the existence of non-Debye-like vibrational modes (boson peak) with a peak energy, E _bp , in the range of 3–7 meV. Both, the boson peak height H _bp and E _bp were found to depend on the composition. Above the boson peak, g(E)/E² exhibits an exponential decrease. Our results demonstrates that the features of the boson peak depend on the amount and type of element M (M = Al, Si, Mg, Sc).     

In-beam Mössbauer study of 57Fe using a secondary 57Mn beam and ion implantation

We have succeeded in obtaining well-resolved M?ssbauer spectra of ⁵⁷Fe arising from short-lived ⁵⁷Mn ( T _1/2 = 1.45 min) in Si and KMnO₄. The M?ssbauer spectra of ⁵⁷Fe in Si are well fitted with a curve consisting of two singlet lines, one being assigned as the interstitial Fe atoms and the other as substitutional ones. The relative intensities of the two lines infer that 60% of ⁵⁷Fe ( ←⁵⁷Mn) atoms land at the interstitial sites and 40% at the substitutional sites at temperatures between 30 K and 296 K. The result for the KMnO₄ sample suggests a presence of an exotic chemical species corresponding to a higher valence state than Fe^{6 +}. Received: 1 May 2001 / Accepted: 4 December 2001     

Mössbauer Spectrometer with Novel Moving System and Resonant Detection of Gamma Rays

Temperature-dependent ⁵⁷Fe Mössbauer spectroscopy has been used to elucidate the hyperfine parameters and dynamical behavior of the metal atom in several organo-iron complexes which have one or more η⁵ P₅ ring structures as ligated groups. The spin-lattice relaxation of the (paramagnetic) one-electron oxidation products occurs on a time scale fast compared to τ_1/2 (ME) at temperatures in the range 85 < T < 320 K.