Exhibition of High- and Low-spin States of the High-temperature Fcc Phase in Nanoparticles of Fe,Fe-rich and Co-rich Alloys

The results of combined X-ray and Mössbauer studies of structure and local magnetic ordering in massive substances Fe, Fe–Ni, Fe–Mn, Fe–Ni–Mn, Fe–Pt, Fe–Co and aerosol nanoparticles produced by their evaporation in rare Ar atmosphere are discussed. This technique provides a stochiometric composition of alloys in nanoparticles. The smallest (5–8 nm) particles for all alloys containing Fe 60–65% are shown to have a bcc structure whereas with doubling a size the particles acquire a fcc structure. This is explained by the fact that by cooling the particles in the course of preparation they quickly reach a state close to the equilibrium and, according to the constitution diagram, must decompose into two phases. Such decomposition in massive alloys was never observed at temperatures below 300°C because of diffusive difficulties. It is found that as-fresh aerosol particles are covered with an X-ray amorphous oxide shell, which is displayed in the room temperature Mössbauer spectra as a superparamagnetic doublet and is transformed into sextet at lower temperatures. An availability of the oxide shell has no practical influence on the particles structure. The obtained Mössbauer spectra are considered with the model suggested by R.J. Weiss in 1963, on existence of two-spin states in the high-temperature fcc modification of Fe and its alloys. Both states coexist, moreover, in the Mössbauer spectra the ferromagnetic state dominates at high temperature and anti-ferromagnetic one at low temperature. The ferromagnetic state manifests itself as a remnant of the frozen magnetic ordering of the high-temperature fcc modification in the resulting bcc structure, whereas the anti-ferromagnetic state is related to some fcc fraction retained under the particles quenching.     

Determination of the Recoilless Fraction in Iron Oxide Nanoparticles Using the Two-lattice Method

We propose a two-lattice method for direct determination of the recoilless fraction using a single room-temperature transmission Mössbauer measurement. The method is first demonstrated for the case of iron and metallic glass two-foil system and is next generalized for the case of physical mixtures of two powders. We further apply this method to determine the recoilless fraction of hematite and magnetite particles. Finally, we provide direct measurement of the recoilless fraction in nanohematite and nanomagnetite with an average particle size of 19nm. A list of values obtained for the recoilless fraction in various materials using the two-lattice method is given.     

Sol-gel derived nanoparticles of Zn substituted lithium ferrite (Li0.32Zn0.36Fe2.32O4): magnetic and Mössbauer effect measurements and their theoretical analysis

Nanoparticles of Zn substituted lithium ferrite (Li_0.32Zn_0.36Fe_2.32O₄) have been prepared by a sol-gel method where the ultra-sonication technique has been adopted to reduce the agglomeration effect among the nanoparticles. The samples were heat-treated at three different temperatures and the formation of the nanocrystalline phase was confirmed by X-ray diffractograms (XRD). The average particle size of each sample has been estimated from the (311) peak of the XRD pattern using the Debye-Scherrer formula and the average sizes are in the range of 10-21 nm. The average particle size, crystallographic phase, etc. of some selected samples obtained from the high-resolution transmission electron microscopy are in agreement with those estimated from the XRD patterns. Static magnetic measurements viz., hysteresis loops, field cooled and zero field cooled magnetization versus temperature curves of some samples carried out by SQUID in the temperature range of 300 to 5 K clearly indicate the presence of superparamagnetic (SPM) relaxation of the nanoparticles in the samples. The maximum magnetization of the SPM sample annealed at 500 °C is quite high (68 Am²/Kg) and the hysteresis loops are almost square shaped with very low value of coercive field at room temperature (827.8 A/m). The particle size, magneto-crystalline anisotropy, etc. have been estimated from the detailed theoretical analysis of the static magnetic data. The dynamic magnetic behavior of the samples was also investigated by observing the ac hysteresis loops and magnetization versus field curves with different time windows at room temperatures. The different soft magnetic quantities viz., coercive field, magnetization, remanance, hysteresis losses, etc. were extracted from dynamic measurements. Dynamic measurements confirmed that the samples are in their mixed state of SPM and ordered ferrimagnetic particles, which is in good agreement with the results of static magnetic measurements. Mössbauer spectra of the samples recorded at room temperature (300 K) and at different temperatures down to 20 K confirmed the presence of the SPM relaxation of the nanoparticles of the samples.     

An estimation of the magnetic disorder at Fe/Cr interfaces in coupled and non-coupled Fe/Cr multilayers

The antiferromagnetic coupling at the Fe/Cr interfaces, inferred from the orientation of the Cr magnetic moments, is used to estimate the magnetic disorder resulting from the interfacial roughness in Fe/Cr multilayers. A crossover from in-plane to out-of-plane orientation of Cr moments depends on the energy cost in either case: (i) to break the interfacial Fe–Cr antiferromagnetic coupling or (ii) having sites with frustrated Cr–Cr antiferromagnetic coupling in the Cr interlayers. A quantitative model of the magnetic frustration due to interfacial disorder in Fe/Cr multilayer systems is described. The step edge density, or terrace size, required to break the interfacial Fe–Cr coupling and destroy the Fe–Fe interlayer exchange coupling is estimated.     

A simple model for the magnetocrystalline anisotropy in mixed ferrite nanoparticles

A simple model, based on the relative occupancy of tetrahedral and octahedral sites by different cations, is proposed for the magnetocrystalline anisotropy of mixed ferrite nanoparticles. According to this model, the total magnetocrystalline anisotropy is the weighted average of the contributions of the anisotropies of Fe³⁺ and M²⁺ ions in A and B sites. The model predictions are confirmed in the case of cobalt-zinc ferrite.     

Mechanochemical Activation of Magnetite Nanoparticles

Using Mössbauer spectroscopy as a function of ball milling time, it was found that nanomagnetite behaves differently than magnetite during mechanochemical activation. The phase sequence is determined by the original particle size of the powder. Magnetite suffers a phase transformation to hematite, while nanomagnetite (d = 19nm) gives rise to superparamagnetism as effect of prolonged milling.     

ANISOTROPIC CHARACTERISTICS OF DEMAGNETIZATION CURVE FOR NANOCRYSTALLINE Nd-Fe-B MAGNET CALCULATED BY MICROMAGNETICS

The demagnetization curves for nanocrystalline Nd-Fe-B magnets of a stoichiometric composition were calculated by making use of the finite element technique of micromagnetics. The curve, especially _iH_c, varies in a wide range with the direction of applied field if the grain number N is taken to be small. With the increase of N, the range becomes smaller and the average of _iH_c decreases and approaches a limit _iH_c(N=∞). _iH_c for finite N is larger than, or at least equal to, _iH_c(N=∞). J_r/J_s is weakly affected by N and the field direction. J_r/J_s(N=∞) decreases with the increase of grain size L. These are larger than the experimental values for the Nd-rich Nd_2.33Fe₁₄B_1.06Si_0.21 magnets by ～0.05. _iH_c(N=∞) increases with the increase of L, and is close to or somewhat smaller than the experimental values of the Nd-rich magnet, as would be expected. In contrast, the curve calculated for the non-interacting grain system (Stoner-Wohlfarth model) of N≥30 depends neither on the field direction nor on N.     

On the origin of discontinuity of the hyperfine fields at Fe nuclei in bulk iron and aerosol Fe nanoparticles

Advancing the early work in which a discontinuity of hyperfine fields at ⁵⁷Fe nuclei in bulk iron and in aerosol Fe nanoparticles has been revealed by analyzing their Mössbauer spectra the present Letter evidences that the existence of several peaks in the hyperfine distribution (HFD) for bulk Fe is caused with the internal magnetic fields owing to its multidomain structure whereas aerosol Fe nanoparticles are single-domain and show only a unique peak in HFD. This argument has been corroborated by transformation of the HFD pattern for Fe foil after applying the external magnetic field of 0.03 T.     

Internal Structure and Magnetic Properties in Cobalt Ferrite Nanoparticles: Influence of the Synthesis Method

The design of novel nanostructured magnetic materials requires a good understanding of the variation in the magnetic properties due to different synthesis conditions. In this work, four different procedures for fabricating Co‐ferrite nanoparticles with similar sizes between 7 and 10 nm are compared by studying their structural and magnetic properties. Non‐aqueous methods based on the thermal decomposition of metal acetylacetonates at high temperatures, either with or without surfactants, provide highly crystalline nanoparticles with large saturation magnetization values and a coherent reversal of the magnetic moment. However, variations in the density of defects and in the shape of the nanocrystals determine the distribution of switching fields and the effective magnetic anisotropy, which reaches up to ≈1 × 10⁷ erg cm^?3 for oleic acid‐capped 9 nm nanoparticles. It is shown that the saturation magnetization values for nanoparticles produced by different methods are in the range between 49 and 95 emu g^?1 due to differences in the stoichiometry, in the cation occupancy, in the magnetic disorder and in the spin canting of the magnetic sub‐lattices, the latter evaluated by in‐field Mössbauer spectroscopy.     

Step-shape angular spin distribution in layered systems by Fe Mössbauer spectroscopy: A general treatment

In the so-called ‘step-shape’ angular spin distribution model for layered systems, the non-collinear directions of the atomic magnetic moments are confined to the film plane and form a homogeneous fan spanning inside an (in-plane) angular interval Δφ centered at an angle φ₀. A general approach for deriving the two parameters φ₀ and Δφ via ⁵⁷Fe Mössbauer spectroscopy measurements is discussed. The analysis extends our previously reported treatment, which assumed that the angular aperture Δφ develops symmetrically versus a fixed direction φ₀ (e.g., the in-plane easy axis of magnetization) oriented either along or perpendicular to the in-plane projection of the Mössbauer γ-ray direction. The proposed approach is also applicable for those cases when not only the spin aperture Δφ is changing but also the aperture center φ₀ is rotating under the influence of different external parameters, such as applied field, temperature, stress, etc. The method is suitable for applications to nanoscale layered heterostructures with in-plane uniaxial or unidirectional magnetic anisotropy. The method is applied to experimental data obtained on a 2-nm thick defected Fe layer with in-plane magnetic texture.     

Effect of Fe substitution on the phase stability and magnetic properties of Mn-rich Ni-Mn-Ga ferromagnetic shape memory alloys

The influence of Fe additions on the martensitic transformation and magnetic properties of Mn-rich Ni-Mn-Ga alloys was investigated by substituting either 1 at% Fe for each atomic species or by substituting Ni with varying amounts of Fe. The magnetic structure of the alloys was studied using ⁵⁷Fe Mössbauer spectroscopy. Mössbauer spectra revealed typical paramagnetic features in Mn-rich Ni-Mn-Ga-Fe alloys owing to the preferential site occupancy of Fe atoms at Ni sites. The evolution of the magnetic properties and phase stability has been correlated with the chemical and atomic ordering in these alloys.     

Phase Composition of Iron Compounds in the Products of Annealing of the Tertiary Basaltic Rock from Góra Obłoga (the Lower Silesia, Poland)

The work presents results of the research on thermal transformations of iron minerals which are present in basalt rock from Góra Obłoga in Pogórze Złotoryjskie District. The rock under study shows microporphyric texture and compact microstructure and contained: olivine, augite, diopside, plagioclases, serpentines, zeolites, apatite and also opaque minerals (oxides). The basalt was annealing within the temperature range between 573–1473 K, in air, and then, microscopic observations, X-ray diffraction as well as Mössbauer spectroscopy measurements were performed. During the heat treatment of the rock it was found that the content of olivine and augite was gradually decreasing due to progressive oxidation of iron compounds, resulting in formation of magnetite and hematite. The comparison of the results of thermal Mössbauer spectral analysis showed that transformation of iron minerals occurred already under conditions when the basic rock mass underwent only insignificant changes.     

Recent developments in the formation and structure of tin-iron oxides by laser pyrolysis

Complex oxides demonstrate specific electric and magnetic properties which make them suitable for a wide variety of applications, including dilute magnetic semiconductors for spin electronics. A tin-iron oxide Sn_1−xFe_xO₂ nanoparticulate material has been successfully synthesized by using the laser pyrolysis of tetramethyl tin-iron pentacarbonyl-air mixtures. Fe doping of SnO₂ nanoparticles has been varied systematically in the 3-10 at% range. As determined by EDAX, the Fe/Sn ratio (in at%) in powders varied between 0.14 and 0.64. XRD studies of Sn_1−xFe_xO₂ nanoscale powders, revealed only structurally modified SnO₂ due to the incorporation of Fe into the lattice mainly by substitutional changes. The substitution of Fe³⁺ in the Sn⁴⁺ positions (Fe³⁺ has smaller ionic radius as compared to the ionic radius of 0.69 Å for Sn⁴⁺) with the formation of a mixed oxide Sn_1−xFe_xO₂ is suggested. A lattice contraction consistent with the determined Fe/Sn atomic ratios was observed. The nanoparticle size decreases with the Fe doping (about 7 nm for the highest Fe content). Temperature dependent ⁵⁷Fe Mössbauer spectroscopy data point to the additional presence of defected Fe³⁺-based oxide nanoclusters with blocking temperatures below 60 K. A new Fe phase presenting magnetic order at substantially higher temperatures was evidenced and assigned to a new type of magnetism relating to the dispersed Fe ions into the SnO₂ matrix.     

Mössbauer spectroscopic studies of the disintegration of hexavalent iron compounds (BaFeO4 and K2FeO4)

Mössbauer spectroscopic studies of BaFeO₄ and K₂FeO₄ as prepared, then either sealed, or exposed to air, or exposed to moist air for a period up to more than one year, were performed at room temperature as a function of time. Some of the samples were studied as a function of temperature down to 4.2 K. K₂FeO₄ and BaFeO₄ after preparation, exhibit a pure Fe⁶⁺ spectrum. K₂FeO₄ shows low stability. After a period of 14 months in a sealed sample holder, the spectrum exhibits 83% noncrystalline Fe³⁺, as Fe₂O₃ nanoparticles, and only 17% of the original Fe⁶⁺. BaFeO₄ sealed, or exposed to dry air disintegrates slowly, exhibiting a spectrum composed of three subspectra. In addition to the original Fe⁶⁺ and final Fe³⁺ subspectra, a subspectrum, of an intermediate stage of a crystalline Fe⁴⁺ system, is present. In the first month the increase of the Fe³⁺ subspectrum is 15%, and that of the Fe⁴⁺ is 8%. BaFeO₄ exposed to moist air, disintegrates at a very fast rate. The Fe³⁺ subspectrum, due to Fe₂O₃ nanoparticles, increases in the first days at the rapid rate of ∼13%/day, and there is no evidence for Fe⁴⁺ in the spectrum. The Fe⁶⁺ in BaFeO₄, Fe³⁺ and Fe⁴⁺ in the disintegrated systems are all magnetically ordered at 4.2 K. Above 90 K the Fe³⁺ subspectra exhibit a superposition of a paramagnetic doublet and a diffuse magnetic sextet, with relative intensities changing with temperature, and changing from sample to sample according to their blocking temperatures, which are determined by the distribution in size of the nanoparticles.     

Frequency Spectra of Quantum Beats in Nuclear Forward Scattering of 57Fe: The Mössbauer Spectroscopy with Superior Energy Resolution

Frequency spectra of quantum beats (QB) in nuclear forward scattering (NFS) are analysed and compared to Mössbauer spectra. Lineshape, number of lines, sensitivity to minor sites, and other specific properties of the frequency spectra are discussed. The most characteristic case of combined magnetic and quadrupole interactions is considered in detail for ⁵⁷Fe. Pure magnetic Zeeman splitting corresponds to a eight-line spectrum of QB, six of which show the same energy separation as the six lines in Mössbauer spectra. Two other lines (called 2′ and 3′) are the lower-energy satellites of the lines 2 and 3. As the quadrupole interaction E _Q appears, the satellites remain unsplit in the quantum beat frequency spectra, as well as the first (zero-frequency) and the 6th (largest frequency) lines. Each of the lines 3 and 5 generates a doublet split by 2E _Q, and the lines 2 and 4 generate triplets. In QB frequency spectra (QBFS) of thin absorbers of GdFeO₃ we demonstrate the enhanced spectral resolution compared to Mössbauer spectra. Small particle size in an antiferromagnet (Fe₂O₃) was found to affect the QBFS via enhancement of the intensity around zero-frequencies. An asymmetric hyperfine field distribution mixes up into the hybridization with dynamical beats, which enlarges the frequencies of the low-lying QBFS lines and makes their shifts relatively large compared to the shift of the highest-frequency line.     

Nuclear resonance reflectivity from a [57Fe/Cr]30 multilayer with the Synchrotron Mössbauer Source

Mössbauer reflectivity spectra and nuclear resonance reflectivity (NRR) curves have been measured using the Synchrotron Mössbauer Source (SMS) for a [⁵⁷Fe/Cr]₃₀ periodic multilayer, characterized by the antiferromagnetic interlayer coupling between adjacent ⁵⁷Fe layers. Specific features of the Mössbauer reflectivity spectra measured with π‐polarized radiation of the SMS near the critical angle and at the `magnetic' maximum on the NRR curve are analyzed. The variation of the ratio of lines in the Mössbauer reflectivity spectra and the change of the intensity of the `magnetic' maximum under an applied external field has been used to reveal the transformation of the magnetic alignment in the investigated multilayer.     

Mössbauer spectroscopic study of the thermal spin crossover in [Fe(II)(isoxazole)6](ClO4)2

The ⁵⁷Fe Mössbauer spectroscopy of mononuclear [Fe(II)(isoxazole)₆](ClO₄)₂ has been studied to reveal the thermal spin crossover of Fe(II) between low-spin (S=0) and high-spin (S=2) states. Temperature-dependent spin transition curves have been constructed with the least-square fitted data obtained from the Mössbauer spectra measured at various temperatures between 84 and 270 K during a cooling and heating cycle. This compound exhibits an unusual temperature-dependent spin transition behaviour with T_C(↓)=223 and T_C(↑)=213 K occurring in the reverse order in comparison to those observed in SQUID observation and many other spin transition compounds. The compound has three high-spin Fe(II) sites at the highest temperature of study of which two undergo spin transitions. The compound seems to undergo a structural phase transition around the spin transition temperature, which plays a significant role in the spin crossover behaviour as well as the magnetic properties of the compound at temperatures below T_C. The present study reveals an increase in high-spin fraction upon heating in the temperature range below T_C, and an explanation is provided.     

Evolution of structural and magnetic properties of FePt/C granular films with thermal annealing

We report the structural and magnetic properties of as-deposited and thermally annealed FePt/C granular multilayer films. The as-deposited system exhibits a disordered fcc FePt phase with an average grain size of 3 nm. Thermal annealing at 650 °C results in partial L1₀ ordering and an associated grain growth to 7 nm. Mössbauer measurements show that there is no non-magnetic component present, suggesting that carbon resides only in the grain boundary region. The ferromagnetic grains are magnetically decoupled.     

Effect of preparation and metal content on the introduction of Fe in BEA zeolite, studied by DR UV-vis, EPR and Mössbauer spectroscopy

Fe-containing SiBEA zeolites were prepared by a two-step postsynthesis method: creation of vacant T-sites by dealumination of tetraethylammonium BEA zeolite with nitric acid and then impregnation of the resulting SiBEA zeolite with an aqueous solution of Fe(NO₃)₃. X-ray diffraction shows that iron is incorporated in SiBEA at lattice sites. The presence of Fe in its oxidation state +3 and at isolated tetrahedral sites for low metal content, was demonstrated by diffuse reflectance UV-vis, EPR and Mössbauer spectroscopy. For high iron content, diffuse reflectance UV-vis and Mössbauer spectra revealed the additional presence of extra-lattice FeO_x oligomers and superparamagnetic Fe-oxyhydroxide. Mössbauer spectroscopy identified superparamagnetic Fe-oxyhydroxide as the main phase when basic conditions are used for the preparation.     

Synthesis,magnetic properties and Mössbauer spectroscopy for the pyrochlore family Bi2BB′O7 with B=Cr and Fe and B′=Nb,Ta and Sb

The samples Bi₂BB′O₇, with B=Cr and Fe and B′=Nb, Ta and Sb were prepared by solid state method. The crystallographic structure was investigated on the basis of X-ray powder diffraction data. Rietveld refinements show that the crystal structure is cubic, space group Fd-3m. The Bi³⁺ cation on the eight-coordinate pyrochlore A-site shows displacive disorder, as a consequence of its lone pair electron con?guration. There is also a considerable A-site disorder shown by Rietveld Analysis and confirmed in the case of the iron containing samples with Mössbauer spectroscopy. The magnetic measurements show paramagnetic behavior at all temperatures for the Cr oxides. The Fe pyrochlores show antiferromagnetic order around 10 K.