Coexisting antiferromagnetism and ferromagnetism in mechanically alloyed Fe-rich Fe–Ni alloys: implications regarding the Fe–Ni phase diagram below 400°C

Fe–Ni alloys below the Invar region with compositions Fe_100−xNi_x (x=21, 24, and 27 at%) were prepared by high-energy ball milling technique (mechanical alloying). The as-milled samples, characterized by X-ray diffraction and Mössbauer spectroscopy, contain a mixture of (BCC) and γ (FCC) phases, whereas the samples annealed at 650°C for 0.5 h show a single γ (FCC) phase displaying a single line Mössbauer spectrum at room temperature (RT). At low temperature, the Mössbauer spectra of annealed Fe₇₆Ni₂₄ and Fe₇₃Ni₂₇ alloys show the existence of a magnetically split pattern together with a broad singlet, which are ascribed to a high-moment ferromagnetic Ni-rich phase and a low-moment Fe-rich phase, respectively. The Fe-rich phase in annealed Fe₇₆Ni₂₄ alloy, which is paramagnetic at RT, undergoes antiferromagnetic ordering at 40 K, estimated from the dramatic line broadening of its spectrum, giving rise to a small hyperfine field (e.g. 2 T at 6 K). The coexistence of these phases is attributed to phase segregation occurring in these alloys as a result of enhanced atomic diffusion. The stability of these alloys towards martensitic (FCC→BCC) transformation at low temperatures is discussed in connection with the Fe–Ni phase diagram below 400°C.     

Remanence of the interparticle interactions and its influence on the microwave absorption in Co-ferrite

Cobalt ferrite nanoparticles were obtained by the sol–gel method at several annealing temperatures: 400, 450, 500, 550 and 600 °C. X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed the formation of the spinel phase with a nanoparticle size in the 17–26 nm range as function of the annealing temperature. The Mössbauer spectra at room temperature showed the presence of a partial inverse spinel structure. Saturation magnetization and the coercive field are strongly dependent on the annealing temperature and they can be associated with variations of the nanoparticles size. Microwave power absorption (MPA) (dP/dH) measurements were carried out as a function of DC field (H_DC) in asymmetric sweeps in the 0 kOeH_DC9 kOe range, at X-band (9.4 GHz), for all annealing temperatures. The large hysteresis in the MPA is due to interparticle interaction associated with its demagnetizing-like nature.     

Magnetic properties of the ternary carbides Tm2Fe17Cx

We have investigated the crystallographic and magnetic properties of the ternary carbides Tm₂Fe₁₇C_x by means of X-ray diffraction, ⁵⁷Fe Mössbauer spectroscopy, ¹⁶⁹Tm Mössbauer spectroscopy and magnetic measurements. It is shown that small amounts of carbon raise the Curie temperature in Tm₂Fe₁₇C_x from below room temperature to about 500 K, at the same time increasing the average Fe moment. Important conclusions regarding the rare-earth sublattice anisotropy were derived from the quadrupole splitting of the ¹⁶⁹Tm Mössbauer spectra and from the strong concentration dependence of the spin reorientation temperature in Tm₂Fe₁₇C_x.     

Superconductivity in non-stoichiometric and tin-substituted La2CuO4: preparation, characterization, Mössbauer and microwave-absorption studies

Two samples of non-stoichiometric La₂CuO₄ were synthesized, one with La/Cu<2, and the other with 10% Sn substituting Cu. They were investigated by X-ray diffraction, Mössbauer spectroscopy, and microwave-absorption techniques. The microwave-absorption data indicated that they were both superconducting, with the transition temperatures T_c of 40.5 and 41.5 K, the one doped with Sn possessing the higher T_c. The Mössbauer spectra revealed that there exist two kinds of Sn(IV) atoms disordered with Cu. Their isomer shift, δ=−0.244(4) mm/s, is in agreement with Sn(IV) coordinated by oxygen. One site was characterized by a single Mössbauer line, being associated with a weakly distorted environment, wherein the Sn, coordinated more symmetrically, is surrounded by four Cu²⁺ ions. On the other hand, the other site, characterized by a Mössbauer doublet exhibited a quadrupole splitting Δ=1.07(2) mm/s, being associated with a highly distorted coordination, explained to be due to Sn occupying two adjacent cationic sites. To our knowledge, such a substitution for copper ions not resulting in a decrease of T_c has not been reported previously.     

Sonochemically assisted synthesis of zinc-doped maghemite

Nanoparticles of zinc-doped maghemite were prepared using ultrasonic radiation. As a precursor, a suspension of maghemite in an alkaline aqueous solution of zinc nitrate at pH 9 was sonicated. The zinc-doped maghemite nanoparticles were investigated by X-ray diffraction, Mössbauer spectroscopy, high-resolution electron microscopy (HREM) and SQUID magnetometry. The Mössbauer measurements, which cover the temperature range 4.2 K to room temperature, were acquired in zero field and an applied field of 5 T. The results show that by using ultrasound radiation, zinc Zn²⁺ can substitute for Fe³⁺ up to a composition close to zinc ferrite (ZnFe₂O₄), which has a random distribution of Fe³⁺ ions over both A and B sublattices in the spinel structure with an inversity parameter of δ = 0.322. This leads to a maximum saturation magnetization (M_s) of 64.1 emu/g at 300 K and 73.5 emu/g at 2 K.     

Handling the particle size and distribution of Fe3O4 nanoparticles through ball milling

A series of samples consisting of spinel Fe₃O₄ nanoparticles with controlled particle sizes and increasing concentration has been obtained through ‘mild’ ball milling (BM) experiments by using an organic carrier liquid. We have succeeded in producing quite narrow particle size distributions with mean values d7–10 nm by an appropriate choice of the milling time for each concentration. The method proved to be practical to tailor the final particle size without formation of undesirable phases. All samples showed superparamagnetic behavior at room temperature, with transition to a blocked state at T_B10–20 K. The mean value and distribution width of the size distributions for the three samples studied were obtained from M(H) cycles recorded at T>T_B showing good agreement with X-ray diffraction and electron microscopy results. The effect of increasing interparticle interactions was to shift T_B upwards, as inferred from magnetization measurements. Mössbauer spectra at low temperatures showed no evidence of enhanced spin disorder.     

Magnetic and structural properties of as-milled and heat-treated bcc-Fe70Cu30 alloy

A ferromagnetic solid solution with a nominal atomic composition Fe₇₀Cu₃₀ and a body-centered structure has been obtained by high-energy ball milling. The decomposition of the system is monitored by X-ray diffraction (XRD), magnetic measurements and Mössbauer spectroscopy. According to XRD, for healing temperatures below 723 K there is only a bcc phase in the material, while for heating temperatures above 723 K a new phase, with a fcc structure, appears, suggesting that the solid solution has decomposed into bcc-Fe and fcc-Cu. However, the magnetic behavior observed during the decomposition process indicates that this evolution is more complex than the simple decomposition into the equilibrium phases. This behavior can be summarized in two points: (1) a decrease in the magnetization at 5 K, and (2) drastic changes in the coercive field with the thermal treatment, soft magnetic behavior for the material in the as-milled state, superparamagnetism for low heating temperatures and a hardening of the material heated to above 723 K, for which the values of the coercive field at room temperature are several times higher than those for the as-milled sample. The Mössbauer spectroscopy performed at room temperature shows that for the heat-treated samples the Fe atoms are in two different phases: a ferromagnetic phase, which evolves to bcc-Fe, and a paramagnetic phase.     

Analysis of atomic arrangement in magnetic Fe–Pt nanoparticles

The order parameter S of Fe–Pt nanoparticles is estimated from X-ray diffraction (XRD) patterns. The total intensity of a diffraction peak is obtained by Rietveld analysis as well as simply integrating the intensity. The Rietveld analysis is found to provide a plausible value of S even for a sample showing an XRD pattern with broad and overlapped peaks. Another order parameter Q, which is obtained from Mössbauer spectra, is introduced, and it is confirmed that Q is equivalent to the probability of Fe atoms being in the L1₀-type atomic arrangement. The coercivity of Fe–Pt nanoparticles is directly proportional to Q, while it vanishes at S=0.4, indicating that the magnetic property of Fe–Pt nanoparticles has a closer relationship to Q than S.     

Investigation of the static and dynamic magnetic properties of CoFe2O4 nanoparticles

We have investigated the magnetic behavior of cobalt ferrite nanoparticles with a mean diameter of 7.2 nm. AC susceptibility of colloidal cobalt ferrite nanoparticles was measured as a function of temperature T from 2 to 300 K under zero external DC field for frequencies ranging from f=10 to 10,000 Hz. A prominent peak appears in both χ′ and χ″ as a function of T. The peak temperature T₂ of χ″ depends on f following the Vogel–Fulcher law. The particles show superparamagnetic behavior at room temperature, with transition to a blocked state at T_B^m94 K in ZFC and 119 K in AC susceptibility measurements, respectively, which depends on the applied field. The saturation magnetization and the coercivity measured at 4.2 K are 27.3 emu/g and 14.7 kOe, respectively. The particle size distribution was determined by fitting a magnetization curve obtained at 295 K assuming a log-normal size distribution. The interparticle interactions are found to influence the energy barriers yielding an enhancement of the estimated magnetic anisotropy, K=6×10⁶ erg/cm³. Mössbauer spectra obtained at higher temperatures show a gradual collapse of the magnetic hyperfine splitting typical for superparamagnetic relaxation. At 4.2 K, the Mössbauer spectrum was fitted with two magnetic subspectra with internal fields H_int of 490, 470 and 515 kOe, corresponding to Fe³⁺ ions in A and B sites.     

Mössbauer study of chromium-substituted nickel ferrites

The structural and magnetic properties of the Cr substituted NiCr_xFe_1−xO₄ (0x1.4) spinel ferrites have been investigated by means of X-ray diffraction and Mössbauer spectroscopy techniques. Their crystal structures are found to be pure cubic phases. The Mössbauer spectra at 295 and 78 K of all samples showed two well-resolved magnetic patterns corresponding to the tetrahedral A-sites and octahedral B-sites. The cation distributions driven from the area under resonance curve of each site revealed that the compounds are gradually transferred from perfect inverse spinel to partially normal spinel structure. The behavior of the magnetic properties as a function of Cr³⁺ concentration has been explained on the basis of the driven cation distribution and it showed that the chrome-rich compositions can be explained in terms of the non-collinear spin model.     

An electron back-scattering Mössbauer spectroscopy study of thin magnetite films

Magnetite films of thickness 16–282 Å were prepared by oxidation of thin ⁵⁷Fe films at 220°C in 5 × 10^-3 Torr oxygen and investigated using electron back-scattering Mössbauer spectroscopy. At room temperature the internal hyperfine fields (H_int) due to the A and B site cations in Fe₃O₄ show a systematic decrease with decreasing film thickness. The spectrum from the 16 Å-thick oxide shows collapse of the magnetic patterns to give a superparamagnetic quadrupole split doublet. All spectra recorded at 12.5 K exhibit six broad peaks of a magnetically split pattern with H_int greater than at room temperature but showing little change with oxide thickness.     

Mössbauer-effect studies of multilayers and interfaces

The usefulness of Mössbauer spectroscopy for the investigation of magnetic multilayer systems is described. By applying ⁵⁷Fe Mössbauer spectroscopy, the behavior of ultrathin magnetic layers, such as FCC-like Fe films on Cu(0 0 1), is studied. Position-specified (depth-selective) information is available by preparing samples in which monatomic ⁵⁷Fe probe layers are placed at specific vertical positions, e.g. at interfaces or at the surface. As demonstrated for epitaxial chemically ordered Fe₅₀Pt₅₀ alloy films and polycrystalline nanostructured Tb/Fe multilayers, the Fe-spin structure can be determined directly, and a site-selective Fe-specific magnetic hysteresis loop can be traced in very-high-coercivity materials. For the studies of non-magnetic layers, on the other hand, hyperfine field observations by ¹⁹⁷Au and ¹¹⁹Sn probes are worthwhile. Spin polarizations in Au layers penetrating from neighboring ferromagnetic 3D layers are estimated ¹⁹⁷Au from Mössbauer spectra and are also studied by inserted ¹¹⁹Sn probes in Au/3D multilayers. In the Sn spectra for Cr/Sn multilayers, it was found that remarkably large spin polarization is penetrating into Sn layers from a contacting Cr layer, which suggests that Cr atoms in the surface layer have a ferromagnetic alignment.     

Ultra short pulse laser annealing of FeB metallic glasses

We present the results of picosecond laser annealing of as-quenched Fe₈₅B₁₅ and Fe₈₂B₁₈ metallic glasses. The influence of the laser radiation on the surface and bulk properties are studied using CrK X-ray diffraction and transmission Mössbauer spectroscopy. The X-ray data show that the amorphous nature of the surface of the samples can be improved with laser treatment. The mat (cooling) surfaces of the ribbons appear to be more affected by the laser treatment, and show a higher stability. The Mössbauer data reveal that laser annealing of ribbon surfaces also affects the bulk properties of these materials due to induced stresses from the surface layer. The magnetic properties of these materials can be modified by laser annealing.     

Magnetic properties in BaFe12O19 nanoparticles prepared under a magnetic field

It was observed that the nanocrystallites of BaFe₁₂O₁₉ formed at 140°C under a 0.25 T magnetic field exhibited a higher saturation magnetization (6.1 emu/g at room temperature) than that of the sample (1.1 emu/g) obtained under zero magnetic field. Both of the two approaches yielded plain-like particles with an average particle size of 12 nm. However, the Curie temperature (T_c), a direct measuring of the strength of superexchange interaction of Fe³⁺–O²⁻–Fe³⁺, increased from 410°C for the nanoparticles prepared without an external field applied to 452°C for the particles formed under a 0.25 T magnetic field, which indicates that external magnetic fields can improve the occupancy of magnetic ions and then increase the superexchange interaction. This was confirmed by electron paramagnetic resonance and Mössbauer spectrum analysis. The results present in this paper suggest that in addition to oxygen defects, surface non-magnetic layer and a fraction of finer particles in the superparamagnetic range, cation vacancies should be responsible for the decreasing of saturation magnetization in magnetic nanoparticles.     

Ultrafine particles of barium ferrite from a citrate precursor

Ultrafine particles of barium ferrite produced by the precursor method have sizes between 5 and 100 nm. These particles have relatively low magnetisations and high coercivities. Mössbauer spectra exhibit different relative areas for the 4f_iv and 2b sites compared to the bulk which partly explains the low magnetisations.     

Investigation of phosphorus surface segregation by X-ray scattering measurements

The surface segregation of phosphorus in silicon at low temperatures is studied by using δ doping structures grown by molecular beam epitaxy. The samples are characterized by X-ray crystal truncation rod (CTR) scattering using synchrotron radiation as the light source. The 1/e decay length of P segregation and segregation barrier energy are obtained by fitting the CTR curves within kinematical approximation of X-ray diffraction theory. The surface segregation of P is strong at a growth temperature of 450 °C, with a 1/e decay length of 14 nm, while for growth temperatures below 350 °C, P segregation is negligible with a 1/e decay length not larger than 4 nm. The segregation barrier energy is determined to be 0.43 eV.     

An investigation of the magnetic order in pseudo binary Co(Ga, Fe) alloys

The results of a Mössbauer effect and a low dc field magnetisation study of the pseudo binary Co₂Ga_2-xFe_x (0.01 x 1.00) alloy system are presented. As a concentration of x=1 is approached, the Fe atoms exhibits a preference for one of two apparently identical Ga sites, resulting in the doubly ordered Heusler structure of the L2₁ type. The critical concentration for the onset of long range ferromagnetic order is x=0.08, with superparamagntic clusters existing either side of this concentration. The size, shape, and interaction between these clusters is strongly dependent on the sample heat treatment. Alloys in the vicinity of this critical concentration, quenched from 830°C, show superparamagnetic behaviour with the magnetic clusters displaying a range of blocking temperatures; whereas alloys given a slow anneal exhibit typical spin-glass freezing.     

Electron irradiation effects on iron-nickel invar alloys

Electron irradiation was used as a means of accelerating the diffusion in Fe-Ni alloys. Mössbauer effect, X-ray and electron microscopy experiments on samples with 28 to 50% Ni show that the Invar character disappears after irradiation up to 250°C, in particular the variation of the lattice parameter versus temperature becomes linear around room temperature. At the same time, two phases appear in the alloy, one rich in nickel and ordered with FeNi (AuCu) superstructure, the other rich in iron and probably ordered (Fe₃Ni). The Invar state is therefore shown to be a metastable state. A diagram of the Fe-Ni alloy is proposed.     

Buffers for high temperature superconductor coatings. Low temperature growth of CeO2 films by metal–organic chemical vapor deposition and their implementation as buffers

Smooth, epitaxial cerium dioxide thin films have been grown in-situ in the 450–650°C temperature range on (001) yttria-stabilized zirconia (YSZ) substrates by metal–organic chemical vapor deposition (MOCVD) using a new fluorine-free liquid Ce precursor. As assessed by X-ray diffraction, transmission electron microscopy (TEM), and high-resolution electron microscopy (HREM), the epitaxial films exhibit a columnar microstructure with atomically abrupt film-substrate interfaces and with only minor bending of the crystal plane parallel to the substrate surface near the interface and at the column boundaries. With fixed precursor temperature and gas flow rate, the CeO₂ growth rate decreases from 10 Å/min at 450°C to 6.5 Å/min at 540°C. The root-mean-square roughness of the films also decreases from 15.5 Å at 450°C to 4.3 Å at 540°C. High-quality, epitaxial YBa₂C₃O_7−x films have been successfully deposited on these MOCVD-derived CeO₂ films grown at temperatures as low as 540°C. They exhibit T_c=86.5 K and J_c=1.08×10⁶ A/cm² at 77.4 K.     

Magnetic properties of xFe2O3(1−x)[B2O3 · PbO] glasses

The magnetic measurements performed on xFe₂O₃(1-x)[B₂O₃ · PbO] glasses show that for x 5 mol.% Fe₂O₃ the thermal variation of reciprocal susceptibility obeys a Curie behaviour. For higher iron content, at T 50 K, a nonlinear variation, typical for systems with random distribution of exchange interactions is observed. At greater temperatures than 50 K a Curie-Weiss behaviour is shown. The composition dependence of the Curie constants is analysed in correlation with the number of Fe³⁺ and Fe²⁺ ions as determined from Mössbauer effect measurements. A comparison with the data obtained in case of xFe₂O₃(1-x)[3B₂O₃ · PbO] glasses is made.