Magnetic hyperfine properties in FeZrB‐type nanocrystalline metallic alloys

Transmission Mössbauer spectra were performed on FeZrB nanocrystalline alloys with high crystalline fraction (≈60%)at temperatures comprised within the range 77–600 K. We report the temperature dependencies of the magnetic hyperfine data of the three contributions: the crystalline bcc‐Fe grains, the residual amorphous phase, and the interface intermediate between the bulk of crystalline and amorphous phases. The evolution of the average value of the hyperfine field characteristic of the residual amorphous phase is discussed in terms of interactions between crystalline grains transmitting through the intergranular phase.     

Ball milling of Fe40Ni40P20-xSix (x = 6, 10 and 14): production and characterization

Progress in the ball milling amorphization of elemental powders with the overall composition Fe₄₀Ni₄₀P_{20 ? x}Si_x (X = 6, 10 and 14) and thermally induced crystallization of obtained alloys were characterized by differential scanning calorimetry, X-ray diffraction and transmission Mössbauer spectroscopy (TMS). Diffusion of Si into Fe and Ni alloys promotes the formation of the amorphous phase, via previous formation of (Fe, Ni) phosphides. After milling for 32–64 h, most of the powders are amorphous but bcc Fe(Si) crystallites remain (about 5% in volume). TMS results indicate that homogenization of the amorphous phase occurs by interdiffusion of Ni and Fe in Fe(Si,P)-rich and Ni(Si,P)-rich zones respectively. Annealing induces structural relaxation of stresses induced by milling, growth of bcc Fe(Si) crystallites, precipitation of bcc Fe(Si) and fcc Ni–Fe, and minor phases of Ni-rich silicides and (Fe, Ni) phosphides. The main ferromagnetic phase is bcc Fe(Si) for Fe₄₀Ni₄₀P₁₀Si₁₀ powders obtained after milling for 32 h. However, it is fcc Fe–Ni for the same alloy after milling for 64 h. In the later powders, as well as for alloys with x = 6 and 14 milled for 32 h, the fcc Fe–Ni shows the Invar magnetic collapse.     

Observation of metastable phase separation and amorphous phase in Fe67Co33 alloy thin films synthesized by pulsed laser depositions

Pulsed laser deposition technique has been used to manipulate the structural order of Fe₆₇Co₃₃ films grown at various substrate temperatures. Films deposited at room temperature exhibited two phases including the stable crystalline phase embedded in the amorphous phase. The crystalline phase separated into two distinct bcc phases as evident from the splitting of (110) reflections, as compared to the bulk counterpart which crystalize into the single phase bcc structure. Both crystalline phases and the amorphous phase were metastable. Films prepared at higher substrate temperatures (∼500 °C), crystallized into the single stable equilibrium bcc structure. Orientation dependent magnetic properties are also presented for the films prepared at both room temperature and higher substrate temperatures. As expected, the easy axes lie parallel to the plane of the substrate due to shape anisotropy. Out of plane magnetization for the films which exhibited short range ordering is found to saturate at smaller field compared to films where single phase bcc structure is stabilized.     

Influence of composition on hyperfine interactions in FeMoCuB nanocrystalline alloy

Influence of varying Fe/B ratio upon hyperfine interactions is investigated in the Fe_91?x Mo₈Cu₁B_x rapidly quenched alloys. They are studied both in the as-quenched (amorphous) state as well as after one-hour annealing at different temperatures ranging from 330 °C up to 650 °C. Such a heat treatment causes significant structural changes featuring a formation of nanocrystalline bcc-Fe grains during the first crystallization step. At higher annealing temperatures, a grain growth of bcc-Fe and occurrence of additional crystalline phases are observed. The relative fraction of the crystalline phase governs the development of magnetic hyperfine fields in the residual amorphous matrix even if this was fully paramagnetic in the as-quenched state. The development of hyperfine interactions is discussed as a function of annealing temperature and composition of the investigated alloys. ⁵⁷Fe Mössbauer spectrometry was used as a principal analytical method. Additional information related to the structural arrangement is obtained from X-ray diffractometry. It is shown that in the as-quenched state, the relative fraction of magnetic hyperfine interactions increases as the amount of B rises. In partially crystalline samples, the contribution of magnetic hyperfine interactions inside the retained amorphous matrix increases with annealing temperature even though the relative fraction of amorphous magnetic regions decreases.     

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.     

Effect of annealing under tensile loading on the structure of nanocrystals in the Finemet alloy

The effect of nanocrystallization annealing under tensile loading on the structure of nanocrystals in the soft magnetic alloy Fe-Si-Nb-B-Cu (Finemet) has been investigated. It has been shown that the body-centered cubic (bcc) lattice of α-FeSi nanocrystals is extended along the direction of the application of the load upon annealing and is compressed in the transverse direction. Nanocrystals in the Finemet alloy have a higher degree of anisotropy of mechanical properties as compared to bulk crystals of α-FeSi, so that agreement between the measured and calculated values of the elongation is achieved only with a significant increase in the elastic moduli. Substantial changes in mechanical properties of the crystals with a decrease in their size to the nanometer scale are caused by the influence of the rigid amorphous matrix of the Fe(Nb)-B phase surrounding the nanocrystals.     

Magnetic properties of soft magnetic composites prepared with crystalline and amorphous powders

Physical properties of soft magnetic composites prepared with a mixture of amorphous (FeSiBC) and crystalline (Fe) powders coated with distinct electrical insulator contents are reported. Density, saturation polarization, permeability and coercivity of the cores reduce linearly with the increase of the softer magnetic phase amount and a general relation can be expressed by a rule of mixtures. The behavior of the coercivity, as a function of the magnetic phase content, differs from that previously reported for magnetic composites prepared with equal amounts of magnetic and non-magnetic phases. For frequencies upto 1 kHz the magnetic losses of the cores are constant, following the same behavior of the coercivity. A qualitative explanation of the behavior of the latter is addressed based on an expression applicable for crystalline and amorphous materials.     

Nanocrystalline iron-based alloys investigated by Mössbauer spectrometry

Nanocrystalline alloys exhibit great fundamental and technological interests because of their microstructural properties, and their excellent soft magnetic properties. ⁵⁷Fe Mössbauer spectrometry is a well suitable technique to investigate Fe-based nanocrystalline alloys: its local probe behaviour permits to elucidate the nature of hyperfine interactions at different resonating iron nuclei and to distinguish their immediate atomic surroundings. We review on the recent Mössbauer developments performed on first FeCuMBSi and then FeCuBSi nanocrystalline alloys. From Mössbauer studies, one can estimate the crystalline (i.e., amorphous) fraction, the Si-content in Fe--Si nanocrystalline grains emerging from amorphous alloys of the first series, the temperature dependence of magnetic behaviours of both crystalline and amorphous phases; finally, we present a novel fitting procedure applied to FeCuBSi nanocrystalline alloys which result from bcc-Fe crystalline grains embedded in an amorphous matrix. In this case, the hyperfine structure is able to model the intergranular phase.     

Study of thickness-dependent magnetic and transport properties of Fe/Al nanostructures

The paper presents magnetic and transport properties of compositionally modulated Fe/Al multilayer structures (MLS), with an overall atomic concentration ratio of Fe:Al = 3:1, 2:1 and 1:1. All MLS show soft ferromagnetic behaviour at room temperature (RT) with an in-plane easy axis of magnetization. In each case, coercivity increases continuously and magnetization decreases with an increase in temperature due to enhancement in the anisotropy as a result of non-uniform and disordered formation of thin intermixed (dead) FeAl layer at the interfaces. The Curie temperature obtained for the MLS is much less than that of bcc Fe but is well above RT. The observed magnetic behaviour is mainly attributed to the formation of different FeAl phases and increase in anti-ferromagnetic interlayer coupling with addition of Al. The formation of these phases is also supported by resistivity results. The results of this research enabled us to understand that by controlling of layers thickness and temperature in multilayer systems, the nanogranular thin films with good resistive and soft magnetic properties can be obtained.     

A critical consideration of magnetism and composition of (bcc) Cu precipitates in (bcc) Fe

Atom probe and small-angle neutron scattering (SANS) measurements were carried out in order to investigate the chemical composition of (bcc) Cu precipitates in a (bcc) Fe matrix. The ratio of nuclear and magnetic integrated intensities (R-value) found by SANS is compared to a theoretical model which is based on the chemical composition obtained from the atom probe data. Furthermore, density functional theory calculations were performed to derive the magnetic moment per atom and the lattice parameters of the Cu alloys modeled in terms of supercells. The calculated and measured R-values agree rather well suggesting that Fe atoms are incorporated in the Cu precipitates up to concentrations of about 50 at.%.     

Dependence of Magnetic Properties on Composition of Nanocrystalline Fe–M–B–Cu (M: Zr,Nb, Mo,Ti, Ta) Alloys

The specialized rf-Mössbauer technique is used to elucidate the magnetic properties of NANOPERM-type nanocrystalline alloys. The influence of alloy composition on the soft magnetic properties is studied for the Fe₈₀M₇B₁₂Cu₁ (M: Ti, Ta, Nb, Mo, Zr) alloys. The rf-Mössbauer experiments allowed us to distinguish magnetically soft nanoclusters from magnetically harder microcrystalline phases. The measurements performed as a function of the rf field intensity allowed the determination of the distribution of anisotropy fields related to the size distribution of bcc nanoclusters. Smaller anisotropy fields in the nanocrystalline phase were found in Nb-, Zr-, and Mo-containing alloys as compared with the alloys which contain Ti and Ta. The Mössbauer measurements were supplemented by X-ray diffraction determination of the size of nanocrystalline grains.     

第一性原理计算Fe从bcc到hcp结构的相变路径及其磁性边界

本文采用基于密度泛函理论的第一性原理方法,计算了压力作用下Fe从bcc到hcp结构相变的势能面、相变路径以及相变过程中的磁性相边界.结果表明:与Burgers路径不同,相变过程中bcc结构(110)bcc面的剪切和相对滑移相互耦合,并伴随有(110)bcc面间距的减小;这一相变机制可以解释Fe的静高压实验中在相变初期观察到的hcp结构异常.因此,并不需要像Wang和Ingalls提出的那样,在相变过程中引入一个亚稳定的fcc相来解释这些实验结果.对相变势能面的计算表明剪切对相变的发生有激活作用.此外,分析表明相变过程中涉及复杂的磁性转变,相变过渡态位置正好位于磁性相边界上,并对原子磁性对结构转变影响的物理机制进行了讨论.     

CEMS investigation of laser melted Fe−Zr alloys

Conversion Electron Mössbauer Spectroscopy (CEMS) studies are reported for as-cut and laser melted surfaces of Fe?Zr ingots in the 25–80 at.% Zr composition range. Disorder and amorphization was observed even on the as-cut surfaces due to the mechanical processing. Besides a significant enhancement of the non-crystalline fraction, surface melting by as laser pulses also results in the appearance of new metastable phases. Solidification via an extremely high cooling rate thus produces amorphous phase in composition ranges where its formation was previously assumed to be restricted to non melt-quenching methods only.     

Evolution of a FeV sigma phase ball-milled in a mixture of argon and air

A coarse-grained sigma phase Fe_48.1V_51.9 was ground in argon in a vibratory mill in the presence of a small but steady air supply. The oxygen content increases regularly at a rate of about 0.25 at.%/h. During the first 140 h of milling, the sigma phase transforms into a heterogeneous bcc alpha phase because of a preferential oxidation of the sole vanadium atoms into V₂O₃. At that milling time, the average composition of the remaining bcc alloy is ~Fe₈₀V₂₀. Mössbauer spectroscopy shows too the presence of an amorphous phase. For longer milling times, ternary Fe–V–O spinel phases do form.     

Molecular Dynamics Study of Stability of Solid Solutions and Amorphous Phase in the Cu-Al System

The relative stability of fee and bcc solid solutions and amorphous phase with different compositions in the Cu-Al system is studied by molecular dynamics simulations with n-body potentials. For CU1-xAlx alloys, the calculations show that the fee solid solution has the lowest energies in the composition region with x 〈 0.32 or x 〉 0.72, while the bcc solid solution has the lowest energies in the central composition range, in agreement with the ball-milling experiments that a single bcc solid solution with 0.30 〈 x 〈 0.70 is obtained. The evolution of structures in solid solutions and amorphous phase is studied by the coordination number （CN） and bond-length analysis so as to unveil the underlying physics. It is found that the energy sequence among three phases is determined by the competition in energy change originating from the bond length and CNs （or the number of bonds）.     

Nanostructures, disordered ferromagnetism and spin glasses

Magnetic systems with a considerable amount of irregular interfaces were investigated by ⁵⁷Fe Mössbauer spectroscopy. Chemically homogeneous ferromagnets around the percolation threshold composition of disappearing magnetism and chemically heterogeneous alloys prepared by nanocrystallization of amorphous alloys belong to this class of materials. Low temperature and high field measurements were performed on nanocrystalline FeZrBCu alloys, on ball‐milled Fe with nano‐size grains and on melt‐quenched amorphous Fe–Zr and Fe–Y alloys in order to clarify the origin of large high‐field susceptibility and to investigate the common features of the approach to magnetic saturation. Curie point determination of the residual amorphous phase in the nanocrystalline FeZrBCu alloys, results on the structure of the nanocrystalline b.c.c. phase and of the interfacial region will be reported.     

非晶态NdxT1-x(T=Fe,Co,Ni)薄膜的低温磁性

本文讨论了非晶态Nd_xT_1-x(T=Fe,Co,Ni)薄膜为滋结构,以及在低温下磁化强度随温度变化的反常特性,在20K附近观测到磁化强度有陡降现象,并且在较大的成份范围内所对应的温度基本不变,我们认为,在这类非晶态合金中,当Nd含量超过一定值后,其磁中性态(通称基态)可能同时是散反铁磁性和散铁磁性的共存态,在20K附近的磁化强度发生陡降,是散反铁磁性←→顺磁性相转变的反映,这两种磁结构共存的临界成份相应约为:Nd-Fe情况x≥0.45;Nd-Co,x≥0.20;Nd-Ni,x≥0.08。 关键词：     

Magnetism of nanocrystalline Finemet alloy: experiment and simulation

Mössbauer spectrometry and magnetic measurements are employed to experimentally investigate the magnetic behavior of nanocrystalline Fe_73.5Cu₁Nb₃Si_13.5B₉ ribbons obtained by appropriate annealing of the amorphous precursor. A detailed analysis of the correlation between the microstructure of annealed samples and their magnetic properties is provided. Thermomagnetic data allow the Curie temperatures of both amorphous residual matrix and nanocrystalline phase to be estimated. The differences between Curie temperatures of amorphous residual matrix and amorphous precursor are investigated and explained in terms of magnetic polarization of the matrix by exchange fields arising from the nanocrystalline grains. Theoretical systems of spins consisting of a single ferromagnetic nanocrystalline grain immersed in weakly ferromagnetic environment, quite similar to our real samples, are considered and their magnetic behavior is investigated by Monte Carlo simulation of low temperature spin ordering, with emphasize on the matrix-nanocrystalline grain interface which is shown to exhibit peculiar magnetic behavior. The magnetic features of the matrix-nanocrystalline grain interface are studied, as depending on matrix-nanocrystalline grain exchange coupling as well as crystalline fraction of the nanocrystalline systems.Received: 10 April 2003, Published online: 4 August 2003PACS: 81.07.Bc Nanocrystalline materials - 75.30.-m Intrinsic properties of magnetically ordered materials - 75.75.+a Magnetic properties of nanostructures     

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.     

Hyperfine interactions on151Eu and57Fe in amorphous EuFe2Si2

The magnetic and quadrupole hyperfine interactions in amorphous EuFe₂Si₂ have been measured using⁵⁷Fe and¹⁵¹Eu Mössbauer spectroscopy. The distributions in the various parameters have been found using the Fourier coefficient method. Novel features of the results are that the Eu charge state (4f occupation number) changes between the crystalline and amorphous phases and that whereas in the crystalline phase neither Eu nor Fe is magnetic, both become so in the amorphous phase.