Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) study of melt-spun Fe85Ga15 ribbons

The local structure in melt-spun Fe₈₅Ga₁₅ ribbons with a width ∼3 mm and thickness ∼60 μm produced in argon atmosphere was studied by analyzing EXAFS and XANES data. The following results were obtained: Ga–Ga bonds were not detected excluding the tendency to form clusters of Ga atoms; Ga substitutes Fe creating a local strain of about +1% on the first shell Fe–Ga bond, whereas on the second Fe–Ga shell strain quickly relaxes down to +0.3%; XANES spectra are compatible with a random substitution of Fe atoms by Ga atoms in the A2 structure. From the AFM investigation, we observed that at the surface (free side) of the ribbon the particles are elongated along the ribbon (∼2 μm×∼5 μm) and each particle is formed by small grains of average size of 200 nm.     

Mössbauer effect study of fine atomic structure of Fe50Al40Ni10 powders

In the present paper, we discuss the local atomic environment of Fe atoms in the mechanically alloyed Fe₅₀Al₄₀Ni₁₀ powders on the basis of hyperfine data estimated from ⁵⁷Fe Mössbauer spectra. B_hf decreases with increasing milling time due to the diffusion of Al and/or Ni into Fe grains. Nickel atoms did not diffuse inside the first coordination sphere of Fe and if the diffusion takes place the number is not more than one atom. Analyses of P(B_hf), indicate that the high hyperfine field values ranging from 30 to 33 T have to be partially attributed to Fe crystalline nanograins and the presence of the defects in them, the hyperfine field values ranging from 15 to 30 T can be associated to the nanocrystalline bcc Fe(Al, Ni) solid solution while the low hyperfine field values (<15 T) result from Fe atoms located in the disordered grain boundaries.     

Influence of alloying additions and annealing time on magnetic properties in amorphous alloys based on iron

The present paper focuses on the influence of alloying additions on magnetostriction coefficient, concentration of free volume and magnetization in Fe–X–Si–B, and Fe–X–Cu–Si–B amorphous alloys. It was shown that in one group of alloys, the enhancement of soft magnetic properties effect can be attributed to formation of nanocrystalline phase αFe(Si), a decrease of the magnetostriction coefficient and annealing out of free volume. In the second group of alloys, this effect is due to a decrease of the magnetostriction coefficient and annealing out of free volume i.e. takes place in the relaxed amorphous phase.     

预退火时间对Fe_(80.8)B_(10)P_8Cu_(1.2)非晶合金微结构及磁性能的影响

研究了预退火时间对Fe_(80.8)B_(10)P_8Cu_(1.2)非晶合金微结构及磁性能的影响.穆斯堡尔谱研究表明:在660 K的预退火温度下,随着预退火时间的增加,Fe原子不断富集,非晶基体中的类Fe_3B化学短程有序结构向类Fe B结构转变,并且非晶基体中Fe第一近邻壳层中Cu原子的逐渐脱离以及Fe-P配位键数量的明显减少可间接表征CuP团簇的形成过程.同时,本研究通过调节预退火时间来调控非晶基体中CuP团簇和Fe团簇的数量,促进后续退火晶化过程中α-Fe纳米晶相的析出,并细化纳米晶尺寸,从而获得综合磁性能更加优异的非晶/纳米晶软磁合金.     

Early precipitation stages of aluminum alloys—The role of quenched-in vacancies

We present preliminary results on the structure of nano-sized particles (clusters of solute atoms or Guinier-Preston-Bagaryatsky (GPB) zones) in aluminum alloys. Hindering the motion of dislocations, these GPB zones (precipitates) are responsible for the strength of AlCuMg-alloys - used e.g. as AA2024 - for the outer shell plates in aircraft industry. We will discuss the role of quenched-in vacancies for the formation and growth of the precipitates. Using positron annihilation (Doppler broadening together with the recently developed tool of high-momentum analysis (HMA)) and X-ray absorption spectroscopy measurements, we are able to characterize the local atomic environment in the vicinity of vacancies and selected elements (Cu) forming the precipitates. The interpretation will be based on a comparison to numerical calculations of positron lifetimes and momentum distributions as well as simulated X-ray absorption spectra. Often reliable numerical calculations of experimental quantities are possible only if relaxed atomic positions - calculated employing an ab-initio code like SIESTA - are used as input.     

Spin-wave spectroscopy study of spatial magnetization fluctuations in metastable nanocrystalline films of Fe-based alloys

The spectrum of standing spin waves is investigated in nanocrystalline Fe films prepared by the pulsed plasma-spraying method. The dispersion relation of these waves is determined in the wave-vector range (0.2–3.2)×10⁶ cm^?1 and is found to be affected by spatial magnetization fluctuations 100 Å in size. These fluctuations are supported as being due to the inhomogeneous distribution of C atoms in the atomic structure of nanocrystalline Fe films.     

High-Energy Ball Milling of Some Intermetallics

High-energy ball milling of metallic powders has been used in recent years for the synthesis of alloys through reactions mainly occurring in solid state. The diffusive phenomena accompanying and promoting the reactions of formation are related to the microstructure acquired by the powders as a consequence of the intense mechanical deformations. The process induces a remarkable comminution of powder particles, inside of which domains of nanometric size are formed and compositional variations often occur. Several analytical techniques are suitable for following the structural evolution of the powders during milling. Among them, Mössbauer spectroscopy is suitable for obtaining detailed local information on the atomic arrangement of the treated materials, if one of the constituents is a Mössbauer isotope, and for detecting little changes occurring at an atomic scale. For these reasons Mössbauer spectroscopy is more sensitive than other analytical techniques especially in the early stages of the process. Some recent results are presented regarding in particular the Fe–Cu, Fe–Al, Fe–Al–Cu, NiAl(Fe) and Fe–Mn systems.     

Mössbauer Spectroscopy Study of Fe–Si Solid Solution Prepared by Mechanical Milling

A specimen of Fe–Si solid solution is prepared by ball milling of proper amounts of the pure elements (3Fe:Si) for different milling times. X-ray diffraction and Mössbauer spectroscopy have been used to characterize the solid solution. The Mössbauer spectra show four different sites corresponding to Fe atoms in a bcc structure having 0, 1, 2 and 3 Si atoms in the 1st nearest-neighbor (nn) shell. The hyperfine magnetic field decreases by 31 kOe for each Si atom in the 1st nn shell. A magnetic component with hyperfine field around (180 kOe) characterized by a broadened sextet was observed which could be due to iron sites having more than 3 Si atoms in the 1st nn. A theoretical model based on the binomial distribution was adopted to analyze the data. Good agreement between the experimental and the theoretical hyperfine field distribution in the high hyperfine field region was found, and the silicon content in the disordered A2 phase is deduced from the parameters which give the best agreement.     

Accounting for nonstoichiometry of niobium carbide NbC y upon milling to a nanocrystalline state

The dependence of the size of particles in the prepared nanocrystalline powders on the composition of nonstoichiometric compounds within their homogeneity intervals has been considered in terms of the high-energy ball milling model. It has been shown that the effect of nonstoichiometry on the milling manifests itself in the concentration dependences of the main characteristics (parameters of the crystal structure, energy of interatomic bonds, elastic properties) of the milled nonstoichiometric compound. The results of model calculations performed for nonstoichiometric cubic niobium carbides NbC _y have been compared with the experimental data on milling of the NbC_0.93 carbide.     

EXAFS study of the atomic structure of amorphous Tb20Fe80

The atomic structure of amorphous Tb₂₀Fe₈₀ thin films has been studied by Extended X-ray Absorption Fine Structure (EXAFS) of both FeK and TbL _III absorption edges. The local site geometry around Fe atoms shows predominantly Fe nearest neighbors with an Fe-Fe distance distribution centered on 2.50±0.02 Å and a coordination number of 9.1±1. In contrast, the radial structure function (RSF) obtained at the Tb edge is broad and asymmetric. The peak in the RSF corresponds to a Tb-Fe near neighbor distance of 2.94±0.1 Å with no evidence for Tb-Tb nearest neighbor coordination. The width and the shape of the RSF suggest that the Tb-Fe atomic environment is anisotropic and strained probably as a consequence of the growth process. This distorted atomic environment is suggested to be responsible for the magnetic anisotropy in these alloys. Thermal annealing at 200 °C leads to reduction inK _u. We propose that this results from reordering of the Tb local environment such that the average structural anisotropy in the distribution is reduced. EXAFS data show that annealing at 400°C causes precipitation of bcc polycrystalline Fe. The addition of 7 at.% Au to the alloy prevents this recrystallization and preserves the amorphous state but does not prevent the structural relaxation which reducesK _u at lower temperatures.     

Probe Mössbauer spectroscopy of the grain boundaries of a Mo-O nanocrystalline system obtained by mechanical alloying

The localization of Fe atoms in the process of mechanical alloying of a Mo powder composite with 8 at % O at boundaries of the bcc Mo grains has been investigated by Mössbauer spectroscopy on impurity ⁵⁷Fe isotope atoms (1 at %), X-ray diffraction, and Auger spectrometry. The process begins with the formation of a nanostructure (～10 nm) in bcc Mo and ends with the formation of a bcc supersaturated solid solution with O atoms at interstitial positions and Fe atoms at substitutional positions. The presence of oxygen in the boundaries of bcc Mo grains leads to an extraordinarily large isomer shift (2 mm/s with respect to α-Fe) for the grainboundary component in the Mössbauer spectrum. This circumstance makes it possible to consider ⁵⁷Fe-O complexes as new probes for studying grain boundaries of powder nanocrystalline materials. As a result, the following three structural components have been identified in the mechanically activated system: a grain boundary and distorted near-boundary regions with the common name interface and a grain with the perfect (defect-free) structure. For powder nanocrystalline (～10 nm) materials subjected to intense mechanical treatment in a planetary ball mill, the widths of the unrelaxed grain boundary and interface average over the entire volume of particles have been experimentally estimated as 0.2 and 1 nm, respectively.     

Large atomic disorder in nanostructured LaNi5 alloys: A La L3-edge extended X-ray absorption fine structure study

Local structure of the nanostructured LaNi₅ alloys, prepared by ball-milling, has been studied using La L₃-edge extended X-ray absorption fine structure spectroscopy. The near-neighbor distances tend to decrease with the ball-milling, and the mean square relative displacements (MSRD) show substantial increase suggesting an increased atomic disorder. High temperature annealing helps in partial recovery of atomic order in the ball-milled samples for milling times upto 20 h, however, the long-time ball-milled samples seems to gain only a local random order. The results suggest that reduced unit-cell volume together with large atomic-disorder might be causing a higher energy-barrier for the hydride-phase formation in the long time ball-milled LaNi₅ powders.     

Neutron diffraction investigation of specific features of the structure of ultrafine (nano) materials

The specific features of the atomic crystal structure of solids with small (<100 nm) sizes of particles in ultrafine (nano) powders have been investigated. It has been shown that, in contrast to the case of coarsegrained materials, distortions of the atomic order occur as an inhomogeneous deformation in surface layers. The distributions of impurity atoms (in the case of a solid solution) and the second phase (in the case of multiphase systems) from the center to the periphery are also inhomogeneous. The atomic distribution function along the radius of a nanoparticle, which characterizes its atomic structure as intermediate between the crystalline and amorphous structures, has been constructed.     

Effects of proton irradiation on structure of NdFeB permanent magnets studied by X-ray diffraction and X-ray absorption fine structure

The effects of proton irradiation on the structure of NdFeB permanent magnet were investigated by X-ray diffraction and X-ray absorption fine structure (XAFS). The results reveal that proton irradiation has no effect on the long-range structure, but significantly affects the atomic local structure of the NdFeB magnet. The alignment degree of the magnet decreases and the internal stress of the lattice increases after proton irradiation. XAFS results show that the coordination number of Fe-Nd in the first neighboring coordination shell of the Fe atoms decreases and the disorder degree increases.     

General regularities of interaction between halogens and surface of fcc metals

Main peculiarities of chemical interaction between halogens and fcc metals have been analyzed and results for chemical reaction on copper and silver surfaces as the most studied ones are discussed. General information about the structure of adsorbed layers on metal surfaces is presented. It has been shown that halogenation occurs in two stages. First, a monolayer of chemisorbed halogen atoms is formed, and then metal halide starts to grow, forming a continuous halide film on the surface. The chlorination of silver is indicated (on the basis of the spectroscopic data) as a unique case due to the possible chlorine dissolution into the substrate bulk. It has also been shown that the use of low-energy electron diffraction is usually ineffective for identification of incommensurate lattices at the stage of monolayer and halide film structure formation. To study incommensurate surface structures and halide nucleation processes on atomic scale, probe microscopy and methods for detecting local structure are necessary.     

Li insertion in ball-milled graphitic carbon studied by total x-ray diffraction

Ball-milled graphitic carbon, both not and electrochemically lithiated, has been studied by total x-ray diffraction involving high-energy synchrotron radiation scattering and atomic pair distribution function analysis. The experimental data has been used to guide reverse Monte Carlo simulations of the three-dimensional structure of the not-lithiated samples. Experimental and modeling results show that ball milling for short times breaks the graphitic layers into smaller pieces as well as generates extended atomic vacancies. Those increase the overall ability of the material to accommodate lithium. Ball milling for longer times keeps generating even more atomic vacancies in the graphitic layers. Carbon atoms displaced from the layers, however, move in between the layers, turning heavily ball-milled graphitic carbon into an assembly of almost-fused-together, heavily buckled layers that have an impaired ability to accommodate Li atoms. This helps explain well the initial substantial increase and then decrease in the Li storage capacity of ball-milled graphitic carbon. The study demonstrates the great ability of total x-ray diffraction to provide precise structural information for complex materials that are being increasingly explored for energy applications.     

Structure and surface layers of Mg-C nanocomposites produced by ball milling

X-ray diffractometry (XRD), X-ray photoelectron spectrometry (XPS), Auger electron spectrometry (AES) and transmission electron microscopy (TEM) were used to investigate the structure and surface layers properties of nanocomposites produced by the mechanical activation (ball milling) of elemental magnesium with carbon materials (amorphous carbon and graphite). Amorphous carbon was synthesized by electric discharge treatment in kerosene. It was shown that ball milling, the allotropic form of carbon materials, and features of hydrogenation have a considerable effect on the structure, surface layer properties, and hydrogen adsorption of a formed composition. XPS and Auger spectroscopy revealed the surface layer of the composite particles to be enriched with carbon. In addition, there were oxide layers on their surfaces due to the particles’ interaction with the environment.     

Mechanism and kinetics of mechanical alloying in an immiscible Fe-Mg system

Mössbauer spectroscopy, X-ray diffraction, Auger spectroscopy, secondary ion mass-spectrometry and chemical analysis were used to study mechanical alloying of Fe and Mg powder mixture with the atomic ratio of 93:7. It has been shown that the process of mechanical alloying involves the formation of nanostructure in α-Fe particles, penetration and segregation of Mg atoms along the α-Fe grain boundaries, formation of the α-Fe(Mg) supersaturated solid solution.     

Spin- and charge density perturbations and short-range order in Fe–Cu and Fe–Zn BCC alloys: A Mössbauer study

A model used to describe the ⁵⁷Fe Mössbauer spectra for the binary BCC iron alloys rich in iron has been extended to account for the alloy crystallographic ordering. The ordering is accounted for by introducing single order parameter. Extension of the model is described in detail. The model has been tested applying it to the Fe–Cu alloys obtained by the arc melting and to the Fe–Zn alloys prepared by the solid state reaction. Random alloys are obtained up to ∼2 at% of Cu, and up to ∼8 at% of Zn. For higher impurity (minor alloy component) concentration it has been found that Cu atoms try to avoid Fe atoms in the iron matrix as nearest neighbors, while the opposite happens to the Zn atoms, albeit at much lesser scale, i.e., Zn–Zn interactions are much weaker than Fe–Zn interactions at the nearest neighbor distance. Perturbations to the iron magnetic hyperfine field (spin density) and electron (charge) density on the iron nucleus have been obtained for both series of alloys versus impurity concentration.     

Coverage-dependent spin reorientation transition temperature of the Fe double-layer on W(1 1 0) observed by scanning tunneling microscopy

The magnetic domain structure of the Fe double-layer on W(1 1 0) is investigated using a variable-temperature scanning tunneling microscope. At low temperature the well-known periodic magnetic stripe domain structure is identified via the observation of domain walls. This is done with a non-spin-polarized tip by taking advantage of a spin–orbit coupling effect. At higher temperature a reorientation to an in-plane easy axis is observed. The spin reorientation temperature is found to be coverage-dependent and it is determined for samples with a coverage of 1.5–2.2 atomic layers of Fe on W(1 1 0).