Nanocrystalline FeAl intermetallics obtained in mechanically alloyed Fe50Al40Ni10 powder

B2-Fe₄₇Al₅₃ intermetallics has been produced by mechanical alloying in a planetary ball mill, using elemental Fe, Al and Ni powder mixture. The microstructural and magnetic properties of the mechanically alloyed Fe₅₀Al₄₀Ni₁₀ powdered samples were investigated by X-ray diffraction and ⁵⁷Fe Mössbauer spectrometry at 300 and 77 K. As resulted from the X-ray diffraction studies, the ordered B2 structure was formed in the Fe₅₀Al₄₀Ni₁₀ powder, together with the bcc α_i-Fe(Al, Ni) (i = 1, 2) solid solutions. Further milling led to a partial disordering of B2-Fe₄₇Al₅₃; it has undergone an order–disorder transition which is characterized by an expansion of the volume Δa₀ (lattice disorder) and a magnetic transition from the paramagnetic to ferromagnetic state which is characterized by strong ferromagnetic interactions in the alloy. The nanocrystalline bcc α_i-Fe(Al, Ni) solid solution was ferromagnetic with a mean crystallite size of 6 nm.     

Evolution of structure, microstructure and hyperfine properties of nanocrystalline Fe50Co50 powders prepared by mechanical alloying

Nanostructured Fe₅₀Co₅₀ powders were prepared by mechanical alloying of Fe and Co elements in a vario-planetary high-energy ball mill. The structural properties, morphology changes and local iron environment variations were investigated as a function of milling time (in the 0-200 h range) by means of X-ray diffraction, scanning electron microscopy (SEM), energy dispersive X-ray analysis and ⁵⁷Fe Mössbauer spectroscopy. The complete formation of bcc Fe₅₀Co₅₀ solid solution is observed after 100 h milling. As the milling time increases from 0 to 200 h, the lattice parameter decreases from 0.28655 nm for pure Fe to 0.28523 nm, the grain size decreases from 150 to 14 nm, while the meal level of strain increases from 0.0069% to 1.36%. The powder particle morphology at different stages of formation was observed by SEM. The parameters derived from the Mössbauer spectra confirm the beginning of the formation of Fe₅₀Co₅₀ phase at 43 h of milling. After 200 h of milling the average hyperfine magnetic field of 35 T suggests that a disordered bcc Fe-Co solid solution is formed.     

Properties of Fe–Ga based powders prepared by mechanical alloying

Alloys of Fe–Ga with starting compositions of 17, 19, 21, 23, and 25 at% Ga and Fe₈₁Ga₁₇Z₂ (Z=Si, Sn) have been prepared by mechanical alloying. Samples were milled in a SPEX Model 8000 mill with a ball to sample weight ratio of about 4:1. Phase formation as a function of milling time has been investigated for the 19 at% Ga sample and suggests that milling times of 12 h produce fully alloyed samples. Alloys have been studied by electron microprobe, X-ray diffraction, vibrating sample magnetometery and ⁵⁷Fe Mössbauer effect spectroscopy. Fully milled powders have measured compositions of Fe_100−xGa_x with x=15.7, 17.0, 19.0, 22.4, and 24.0 and Fe_83.1Ga_15.2Z_1.7 (for both Z=Si and Sn). X-ray diffraction showed the presence of a disordered bcc phase with no indication of an ordered D0₃ phase. However, the latter is difficult to observe with X-ray diffraction because of the low intensity of the fcc superlattice peaks. A bimodal Fe hyperfine field distribution as obtained from Mössbauer effect spectra indicated the presence of two discrete Fe environments. The results suggested a lower degree of Ga clustering than has been previously observed in Fe–Ga alloys, of similar composition, prepared by melt spinning. The microstructure is similar to that of Fe–Ga thin films prepared by combinatorial sputtering. Some samples have also been studied after annealing at 800 °C for 8 h. No changes were observed in X-ray diffraction patterns after annealing. However, Mössbauer effect studies show the formation of D0₃ and L1₂ order in annealed samples analogous to the phases observed in melt spun ribbons of similar composition.     

Synthesis and characterization of the xZnO-(1−x)α-Fe2O3 nanoparticles system

The xZnO-(1−x)α-Fe₂O₃ nanoparticles system has been obtained by mechanochemical activation for x=0.1, 0.3 and 0.5 and for ball milling times ranging from 2 to 24 h. Structural and morphological characteristics of the zinc-doped hematite system were investigated by X-ray diffraction (XRD) and Mössbauer spectroscopy. The Rietveld structure of the XRD spectra yielded the dependence of the particle size and lattice constant on the amount x of Zn substitutions and as function of the ball milling time. The x=0.1 XRD spectra are consistent with line broadening as Zn substitutes Fe in the hematite structure and the appearance of the zinc ferrite phase at milling times longer than 4 h. Similar results were obtained for x=0.3, while for x=0.5 the zinc ferrite phase occurred at 2 h and entirely dominated the spectrum at 24 h milling time. The Mössbauer spectra corresponding to x=0.1 exhibit line broadening as the ball milling time increases, in agreement with the model of local atomic environment. Because of this reason, the Mössbauer spectrum for 12 h of milling had to be fitted with two sextets. For x=0.3 and 12 milling hours, the Mössbauer spectrum reveals the occurrence of a quadrupole-split doublet, with the hyperfine parameters characteristic to zinc ferrite, ZnFe₂O₄. This doublet clearly dominates the Mössbauer spectrum for x=0.5 and 24 h of milling, demonstrating that the entire system of nanoparticles consists finally of zinc ferrite. As ZnO is not soluble in hematite in the bulk form, the present study clearly demonstrates that the solubility limits of an immiscible system can be extended beyond the limits in the solid state by mechanochemical activation. Moreover, this synthesis route allowed us to reach nanometric particle dimensions, which would make the materials very important for gas sensing applications.     

Role of Cr ions on superexchange coupling in α-Fe2O3 nanoparticles

Synthesis of nanocomposites of iron oxide & chromium oxide (α-Fe₂O₃–Cr₂O₃) with different concentrations was carried out by a wet-chemical method and the structural, optical and hyperfine properties have been investigated. The prepared nanocomposites were characterized by powder X-ray diffractometry (PXRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV–VIS spectroscopy, Fourier transformed infrared (FTIR) spectroscopy and Mössbauer spectroscopy. XRD measurements confirmed the formation of pure phase composites having particle sizes in nanometer regime. The same has been corroborated by TEM micrographs, which revealed that the formation of monodispersed nanocomposites have the average particle size 44 nm. Mössbauer study of the samples showed the transition of iron oxide from anti-ferromagnetic state to paramagnetic state having a typical relaxation in the spectrum with increasing concentration of Cr₂O₃.     

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.     

Mössbauer spectroscopic studies of Fe-20 wt.% Cr ball milled alloy

Interesting differences were noticed in the alloying process during ball milling of Fe-10 wt.% Cr and Fe-20 wt.% Cr alloys by ⁵⁷Fe Mössbauer spectroscopic studies. In both cases, there is almost no diffusion of Fe in Cr or vice versa up to 20 h of milling time. As the powders are milled for another 20 h substantive changes occur in the Mössbauer spectra showing atomic level mixing. But the two compositions behave differently with respect to alloying. Fe-20 wt.% Cr sample does not differ much in the hyperfine field distribution as it is milled from 40 to 100 h. On the other hand, the hyperfine field distribution keeps on changing with milling time for Fe-10 wt.% Cr sample even up to 100 h of milling. The average crystallite size is found to be 7.5 nm for Fe-10 wt.% Cr and 6.5 nm in Fe-20 wt.% Cr after milling.     

Mixing of iron with various metals by high-energy ball milling of elemental powder mixtures

The alloying of Fe with T=V, Cr and Mn by high-energy ball milling of elemental powder mixtures has been studied from the scale of a powder particle down to the atomic scale using X-ray and neutron diffraction, Mössbauer spectrometry and magnetic measurements for Fe_1?x T _x alloys with x=0.50, 0.65 for T=V, x=0.50, 0.70 for T=Cr and x=0.72 for T=Mn. Different alloying behaviours are observed according to T once powder particles have the final composition. The rather fast mechanical alloying of Fe with Mn reflects the statistical nature of the milling process in contrast to the slow mixing of Fe with V and of Fe with Cr. Hyperfine magnetic field distributions remain stationary in shape in the last milling stage at room temperature both for T=V and T=Cr. Magnetic measurements evidence the persistence with milling time of a large population of nanometer-sized Fe-Cr zones that are superparamagnetic at room temperature and at 400 K. By contrast, room-temperature Mössbauer spectra show only a single line for long milling times. The unmixed stationary state of milled p-Fe_0.7Cr_0.3 is discussed in the light of a recent model of systems driven by competing dynamics.     

Mössbauer and PAC studies of nanocrystalline Fe

High-purity Fe powder was mechanically milled under argon at ambient temperature using an SPEX 8000 mill. The local atomic and magnetic structure was studied using⁵⁷Co/Fe Mössbauer and¹¹¹In/Cd perturbed angular correlations (PAC) spectroscopies. After 32 hours of milling, X-ray diffraction revealed effective grain diameters of 18 nm and energy-dispersive X-ray analysis indicated a Cr impurity concentration of 5%, presumably introduced by mechanical attrition of steel ball bearings used for milling. In addition to a spectral component very similar to bulk iron metal, the Mössbauer spectra exhibited hyperfine field shifts attributed to the Cr impurities. PAC spectra on Fe milled for 5 h, with no contamination, exhibited two components: (1) A slightly broadened magnetic interaction attributed to interior, defect-free sites of In/Cd probes with a mean hyperfine field slightly greater than in macroscopic grains. The defect-free site fraction grew appreciably during milling, even though In is essentially insoluble in Fe. (2) An indistinct signal due to mixed magnetic and quadrupole interactions attributed to probes at surface or other defect sites.     

Heat generation ability in AC magnetic field of nano MgFe2O4-based ferrite powder prepared by bead milling

Nanosized MgFe₂O₄-based ferrite powder having heat generation ability in an AC magnetic field was prepared by bead milling and studied for thermal coagulation therapy applications. The crystal size and the particle size significantly decreased by bead milling. The heat generation ability in an AC magnetic field improved with the milling time, i.e. a decrease in crystal size. However, the heat generation ability decreased for excessively milled samples with crystal sizes of less than 5.5 nm. The highest heat ability (ΔT=34 °C) in the AC magnetic field (370 kHz, 1.77 kA/m) was obtained for fine MgFe₂O₄ powder having a ca. 6 nm crystal size (the samples were milled for 6-8 h using 0.1 mm ? beads). The heat generation of the samples was closely related to hysteresis loss, a B-H magnetic property. The reason for the high heat generation properties of the samples milled for 6-8 h using 0.1 mm ? beads was ascribed to the increase in hysteresis loss by the formation of a single domain. Moreover, the improvement in heating ability was obtained by calcination of the bead-milled sample at low temperature. In this case, the maximum heat generation (ΔT=41 °C) ability was obtained for a ca. 11 nm crystal size sample was prepared by crystal growth during the sample calcination. On the other hand, the ΔT value for Mg_0.5Ca_0.5Fe₂O₄ was synthesized using a reverse precipitation method decreased by bead milling.     

Effect of mechanical milling on the magnetic properties of garnets

Rare earth garnets after milling to nanosizes are found to decompose into rare earth orthoferrite and other rare earth and iron oxide phases. The magnetization for the yttrium iron garnet decreases in the nano state due to the formation of antiferromagnetic phases. But for the gadolinium iron garnet when milled up to 25 h, the room temperature magnetization increases despite the formation of antiferromagnetic and non-magnetic phases. This is attributed to the uncompensated moments of the sublattices because of the weakening of the superexchange interaction due to change in bond angles and the breaking of some superexchange bonds on account of the defects and oxygen vacancies introduced on milling. For the 10 h milled gadolinium iron garnet at 5 K, after correcting for the non-magnetic phases present, there is an increase in the magnetic moment of about 10% as compared to the value for the as-prepared garnet. The magnetic hyperfine fields corresponding to the various phases were measured using ⁵⁷Fe Mössbauer spectroscopy at 16 K. The isomer shift values indicate the loss of oxygen for the samples milled for larger duration.     

Mössbauer and X-ray diffraction studies of mechanically alloyed Fe-Al

Powder samples of Fe₂₅Al₇₅ were prepared by the mechanical alloying method. Mössbauer effect, X-ray diffraction and DSC measurements indicate that Fe and Al crystalline powder transform into Fe-Al amorphous powder with increasing milling time. The X-ray diffraction patterns of the milled Fe₂₅Al₇₅ do not clearly show a sign of the existence of the intermetallic phases or Fe-Al solid solution. However, Mössbauer measurements reveal two sites with hyperfine magnetic fields 30.2 and 26.0 T. These sites form locally during the milling process and then they disappear.     

First-principles study on the electronic structure, magnetic properties and phase stability of alloyed cementite with Cr or Mn

Using the first-principles technique, the electronic structures, magnetic properties and phase stability of alloyed cementite with Cr or Mn were investigated. The calculations show that the chemical and mechanical stability of alloyed cementite can be strengthened by the use of Cr/Mn-doped method. The Magnetic Moments (Ms) of Mn₁Fe₂C, Mn₂Fe₁C, Cr₁Fe₂C and Cr₂Fe₁C are 5.274, 0.941, 1.864 and 0.736 μ_B/f.u, respectively. The Ms of Cr in Fe₂CrC (−1.374 μ_B) and Cr₂FeC (−0.032 μ_B) are different due to replacing different sites Fe atoms. The magnetic behaviors of Mn are different from Cr in alloyed cementite. The Ms of Mn in Fe₂MnC and Mn₂FeC are 2.300 μ_B and −0.147 μ_B, respectively.     

Novel carbon nanotube iron oxide magnetic nanocomposites

A novel magnetic nanocomposite of γ-Fe₂O₃ nanoparticles decorated multiwalls carbon nanotubes (MWNTs) was synthesized for the first time by a simple chemistry precipitation method. The structure and morphology of the composite was characterized by X-ray powder diffractometer (XRD), TEM and EDS. The results of XRD and TEM show that γ-Fe₂O₃ nanoparticles is immobilized on the side wall of the MWNTs, the size of most of the particle is <5 nm.The EDS analysis shows that the atomic ratio of Fe to O is 2:3. The magnetization curves of the MWNTs and γ-Fe₂O₃ decorated MWNTs were measured by VSM at room temperature, which indicate that the saturated magnetization (Ms), remanence (Mr) and coercivity (Hc) of the decorated MWNTs are much larger than those of MWNTs, and the decorated MWNTs exhibit well magnetic properties.     

Properties of Cr-substituted M-type barium ferrites prepared by nitrate–citrate gel-autocombustion process

The Cr-substituted M-type barium hexaferrites, BaFe_12−xCr_xO₁₉, with x=0.0–0.8$x=0.0–0.8$ have been successfully prepared by nitrate–citrate auto-combustion process using citric acid as a fuel/reductant and nitrates as oxidants. The resulting precursors were calcined at 1100 °C for 1 h and followed by sintering at 1200 °C for 12 h in oxygen atmosphere. The ferrites were systematically investigated by using powder X-ray diffractometer (XRD), magnetic hysteresis recorder, Mössbauer spectrometer, and scanning electron microscope (SEM). The XRD data show the formation of pure magnetoplumbite phase without any other impurity phases. Both a and c lattice parameters calculated by the Rietveld method systematically decrease with increasing Cr content. The effects of Cr³⁺ ions on the barium ferrites were reported and discussed in detail. The site preference of Cr³⁺ and magnetic properties of the ferrites have been studied using Mössbauer spectra and hystereses. The results show that the magnetic properties are closely related to the distributions of Cr³⁺ ions on the five crystallographic sites. The saturation magnetization systematically decreases, however, the coercivity increases with Cr concentration. The magnetization and Mössbauer results indicate that the Cr³⁺ ions preferentially occupy the 2a, 12k, and 4f_VI sites. The average size of hexagonal platelets obtained by SEM photographs tends to decrease with respect to Cr content.     

High heat generation ability in AC magnetic field for nano-sized magnetic Y3Fe5O12 powder prepared by bead milling

Nano-sized magnetic Y₃Fe₅O₁₂ ferrite having a high heat generation ability in an AC magnetic field was prepared by bead milling. A commercial powder sample (non-milled sample) of ca. 2.9 μm in particle size did not show any temperature enhancement in the AC magnetic field. The heat generation ability in the AC magnetic field improved with a decrease in the average crystallite size for the bead-milled Y₃Fe₅O₁₂ ferrites. The highest heat ability in the AC magnetic field was for the fine Y₃Fe₅O₁₂ powder with a 15-nm crystallite size (the samples were milled for 4 h using 0.1 mm? beads). The heat generation ability of the excessively milled Y₃Fe₅O₁₂ samples decreased. The main reason for the high heat generation property of the milled samples was ascribed to an increase in the Néel relaxation of the superparamagnetic material. The heat generation ability was not influenced by the concentration of the ferrite powder. For the samples milled for 4 h using 0.1 mm? beads, the heat generation ability (W g⁻¹) was estimated using a 3.58×10⁻⁴ fH² frequency (f/kHz) and the magnetic field (H/kA m⁻¹), which is the highest reported value of superparamagnetic materials.     

Preparation of α-Fe2O3 nanoparticles by high-energy ball milling

α-Fe₂O₃ nanoparticles were prepared by high-energy ball milling using α-FeOOH as raw materials. The prepared samples were characterized by transmission electron microscopy (TEM), Mössbauer spectroscopy, X-ray diffraction (XRD) and differential thermal analysis–thermogravimetric analysis (DTA–TGA). The results showed that after 90 h milling α-Fe₂O₃ nanoparticles were obtained, and the particle size is about 20 nm. The mechanism of reaction during milling is supposed that the initial α-FeOOH powder turned smaller and smaller by the high-speed collision during ball milling, later these particles turned to be superparamagnetic, at last these superparamagnetic α-FeOOH particles were dehydrated and transformed into α-Fe₂O₃.     

Size dependence of the magnetic and hyperfine properties of nanostructured hematite (α-Fe 2 O 3 ) powders prepared by the ball milling technique

In this work we present the study of hematite (α-Fe₂O₃) nanostructures synthesized by the ball milling technique. The structural characterization and the crystallite size estimation have been carried out using the X-ray diffraction (XRD) technique. Data analyses indicate that the hematite phase (space group, R-3C) is preserved after the milling process. As the milling time is increased, a second phase (α-Fe) appears. The mean crystallite size shows a decreasing tendency as the milling time is increased. High-resolution transmission electron microscopy (HRTEM) images show the formation of grains composed of crystallites with irregular shapes. Mössbauer spectra of milled powders carried out at 297 and 77 K are well modeled with a histogram distribution of hyperfine fields. The presence of one additional sextet which corresponds to the ∝-Fe phase is also determined in agreement with XRD data analysis. Magnetic measurements suggest the suppression of the Morin transition in the milled samples and the absence of thermal relaxation effects in agreement with the Mössbauer spectroscopy results.     

Composition, microstructure, and properties of CrNx films deposited using medium frequency magnetron sputtering

CrN_x films were deposited on stainless steel and Si (1 1 1) substrates via medium frequency magnetron sputtering in a N₂ + Ar mixed atmosphere. The influence of N₂ content on the deposition rate, composition, microstructure, mechanical and tribological properties of the as-deposited films was investigated by means of the X-ray photoelectron spectrometry (XPS), X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), nanoindentation and tribometer testing. It was found that the N atomic concentration increased and the phase transformed from a mixture of Cr₂N + Cr(N) to single-phase Cr₂N, and then Cr₂N + CrN to pure CrN phase with the increase of N₂ content. The Cr 2p_3/2 and N 1s of XPS spectra also confirmed the evolution of phase. Accordingly, all films exhibited a typical columnar structure which lies in the zone T of Thornton Model. The mixed Cr₂N and Cr(N) phases showed low hardness and high friction coefficient. Cr₂N possessed higher hardness than CrN while CrN exhibited lower friction coefficient.     

Mechanosynthesis of nanocrystalline MgFe2O4—neutron diffraction and Mössbauer spectroscopy

The evolution of nanocrystalline n-MgFe₂O₄ by high-energy milling a mixture of MgO and α-Fe₂O₃ for periods of between 0 h and 12 h has been investigated by neutron diffraction in addition to previous Mössbauer, XRD and HRTEM measurements. Complete transformation of the milled products to n-MgFe₂O₄ only occurs on milling to ～8 h even though the average particle size decreases to <?～10 nm after milling for 2 h. The applied field Mössbauer spectra of n-MgFe2O4 can be well described by two subspectra representing core and shell regions with different cation distributions and spin canting angles. The neutron pattern of nanocrystalline MgFe₂O₄ is described well by two components comprising nanoparticles of core and shell dimensions ～7(1) nm and ～0.7(1) nm, respectively, in support of the Mössbauer core-shell model.