Nanocrystalline Fe/Zr alloys: preparation by using mechanical alloying and mechanical milling processes

Nanocrystalline Fe/Zr alloys have been prepared after milling for 9 h the mixture of elemental Fe and Zr powders or the arc-melting produced Fe₂Zr alloy by using mechanical alloying and mechanical milling techniques, respectively. X-ray and Mössbauer results of the Fe and Zr powders, mechanically alloyed, suggest that amorphous Fe₂Zr phase and $\upalpha$ -Fe(Zr) nanograins have been produced with relative concentrations of 91% and 9%, respectively. Conversely, the results of the mechanically milled Fe₂Zr alloy indicate that nanograins of the Fe₂Zr alloy have been formed, surrounded by a magnetic inter-granular phase that are simultaneously dispersed in a paramagnetic amorphous phase.     

Amorphization of the intermetallic phase CoZr by mechanical grinding

The intermetallic phase CoZr was milled in a planetary ball mill. X-ray diffraction shows that the crystalline Bragg reflexes vanish totally with increasing milling period while simultaneously a broad maximum appears, attributed to a developing amorphous phase. To amorphize the intermetallic phase completely it takes a relatively long milling period (100 h), whereas a powder mixture of the elements of 50 at% Co and 50 at% Zr is already completely amorphized after 8 h of mechanical alloying. Both amorphous powders produced by different starting materials show identical properties by means of X-ray diffraction, measurement of the released crystallization enthalpy, the absolute specific heat capacity, and Mößbauer spectroscopy. TEM analysis of the intermetallic phase confirms the simultaneous presence of amorphous and remaining crystalline grains after short milling periods and the complete amorphization after long milling periods. A possible explanation for the amorphization process of the compound may be the accumulation of internal strain in the crystalline grains during the milling process. Another possible explanation may be the addition of iron impurities to the stoichiometric compound due to the wear debris of the milling balls and the milling vials of stainless steel.Dedicated to Professor Dr. phil., Dr. h.c. mult. Friedrich Hund on the occasion of his 95^th birthday     

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.     

The first principle study of magnetic properties of Mn2WSn,Fe2YSn (Y=Ti,V), Co2YSn (Y=Ti,Zr, Hf,V, Mn) and Ni2YSn (Y=Ti,Zr, Hf,V, Mn) heusler alloys

The spin polarized electronic band structures, density of states (DOS) and magnetic properties of Mn₂WSn, Fe₂YSn (Y=Ti, V), Co₂YSn (Y=Ti, Zr, Hf, V, Mn) and Ni₂YSn (Y=Ti, Zr, Hf, V, Mn) huesler compounds are reported. The calculations are performed by using full-potential linearized augmented plane wave method (FP-LAPW) within density functional theory. The magnetic trend in these compounds is studied using values of magnetic moments, exchange interaction and calculated band gap. The results reveal that Mn₂WSn and Ni₂VSn show 100% spin polarization, Co₂YSn (Y=Ti, Zr, Hf, Mn), Fe₂YSn (Y=Ti, V), and Ni₂MnSn exhibit metallic nature and Ni₂YSn (Y=Ti, Zr, Hf) and Co₂VSn show semi-conducting behavior.     

Magnetoresistance and magnetostriction of Co2Cr0.6Fe0.4Al Heusler alloy

We report a study of the magnetotransport properties of the Co₂Cr_0.6Fe_0.4Al Heusler alloy grown by means of the arc-melting technique. X-ray diffraction and energy dispersive X-ray spectroscopy have been used to analyze the crystallographic structure and the sample stoichiometry. Temperature-dependent magnetization measurements have been carried out in the range 300-850 K. Co₂Cr_0.6Fe_0.4Al is theoretically predicted to have full positive spin polarization at the Fermi level, and as a consequence its spin-dependent transport properties are being intensively studied. Low field magnetoresistance exceeding 30% has been observed very recently in Co₂Cr_0.6Fe_0.4Al compact pellets. We have performed magnetoresistance and magnetostriction measurements in both the as-grown alloy and compact pellets made of mechanically milled Co₂Cr_0.6Fe_0.4Al. The as-grown and the milled sample show negligible anisotropic magnetostriction (25 μst at saturation), whilst only the milled sample exhibits magnetoresistance (0.65% at 300 K). These results permit us to discard the magnetostrictive effects as the magnetoresistance source.     

Structural evolutions of the mechanically alloyed Al<Subscript>70</Subscript>Cu<Subscript>20</Subscript>Fe<Subscript>10</Subscript> powders

Elemental mixtures of Al, Cu, Fe powders with the nominal composition of Al₇₀Cu₂₀Fe₁₀ were mechanically alloyed in a planetary ball mill for 80 h. Subsequent annealing of the as-milled powders were performed at 600–800°C temperature range for 4 h. Structural characteristics of the mechanically alloyed Al₇₀Cu₂₀Fe₁₀ powders with the milling time and the heat treatment were investigated by X-ray diffraction (XRD), differential scanning calorimeter (DSC) and differential thermal analysis (DTA). Mechanical alloying of the Al₇₀Cu₂₀Fe₁₀ did not result in the formation of icosahedral quasicrystalline phase (i-phase) and a long time milling resulted in the formation of β-Al(Cu,Fe) solid solution phase (β-phase). The i-phase was observed only for short-time milled powders after heat treatment above 600°C. The β-phase was one of the major phases in the Al₇₀Cu₂₀Fe₁₀ alloy. The w-Al₇Cu₂Fe₁ phase (w-phase) was obtained only after heat treatment of the short-time milled and unmilled samples. The present investigation indicated that a suitable technique to obtain a large amount of quasicrystalline powders is to use a combination of short-time milling and subsequent annealing.     

Hyperfine interactions and local magnetic ordering in Zr(Fe1-xCox)2 (0⩽x⩽0.2)

In the pseudobinary intermetallic compounds Zr(Fe_1-xCo_x)₂ (0?x?0.2) the hyperfine fields of all nuclei present are investigated by means of Mössbauer effect and NMR. While for the “nonmagnetic” site the Zr-hyperfine field depends on the configuration of the nearest Fe, Co neighbours, no such effect is observed for the hyperfine fields on the “magnetic” sites. A large pseudodipolar interaction is observed for the Fe and Co atoms, from which the coexistence of several directions of magnetization can be deduced. The easy direction seems to be determined by the respective Fe/Co configuration.     

The effect of Fe doping on superconductivity in ZrRuP

This work reports the structure and superconducting properties of the superconductor ZrRuP doped with Fe; the ZrRu_1−xFe_xP solid solution was investigated by means of X-ray powder diffraction, SQUID magnetometry and Mößbauer spectroscopy. It is shown that the modification of the superconducting properties by doping with Fe is similar to the effect of chemical pressure and that the Fe doped compounds do not show any magnetic ordering.     

X-ray Debye temperature of mechanically milled Ni0.5Zn0.5Fe2O4 spinel ferrite

The X-ray Debye temperatures, θ _M , of spinel ferrite composition Ni_0.5Zn_0.5Fe₂O₄, mechanically milled upto 9 hrs, were determined from integrated intensities of selected Bragg reflections. The θ _M was found to increase with milling time. The results are explained in the light of milling induced grain orientation and surface effect. The values of θ _M were found to be lower as compared to the Debye temperatures obtained from infrared spectral data analysis. The difference can be explained on the basis of increase in an excess free volume in the form of vacancies and vacancy clusters associated with grain boundaries.     

Enhancement of the recoilless fraction in R2Fe10Co4Si2 (R=Gd, Er, Y) offstoichiometric compounds after hydrogenation

Samples of R₂Fe₁₀Co₄Si₂ (R=Gd, Er and Y) solid solutions were prepared by arc melting and exposed to hydrogenation. Characterization of hydrogenation effects was done using Mössbauer spectroscopy. The values of the magnetic hyperfine fields corresponding to the four inequivalent lattice sites were found to increase after hydrogenation in all offstoichiometric compounds investigated. Slight changes in the relative site occupancies were observed. Transmission Mössbauer spectra were also recorded for absorbers consisting of the intermetallic and the stainless steel etalon. The recoilless fraction was derived from these spectra using the method developed by us. Our study is the first to evidence that the recoilless fraction is enhanced after hydrogenation.     

Spontaneous volume magnetostriction in Y(Fe1−xCox)2 and Zr(Fe1−xCox)2

The spontaneous volume magnetostriction is calculated for Y(Fe_1?xCo_x)₂ and Zr(Fe_1?xCo_x)₂ in the simple itinerant-electron model. The density of states for various compositions is calculated by the recursion method. The calculated results on the composition dependence of the spontaneous volume magnetostriction are shown to be consistent with the experimental ones.     

Mössbauer study of Fe powder mechanically alloyed by power ultrasonics

The Mössbauer and transmission electron microscopy (TEM) analysis of Fe-powder and Fe₄₆C₅₄-powder blend, mechanically milled by high power ultrasonics (USM) in He environment for 20–75 hours, have been carried out. As shown, the USM results in effective grinding of initial polycrystalline iron particles up to formation of single crystalline state, dissolution of carbon in iron particles, synthesis of carbides and possibly penetration of Fe atoms into graphite. Annealing of processed Fe₄₆C₅₄ powder causes carbide reaction.     

Solid state amorphization reaction in Fe−Zr multilayers

The solid state reaction of thin multilayered Fe?Zr films has been studied by means of Conversion Electron Mössbauer Spectroscopy and Rutherford Backscattering. The results for the samples with the overall composition Fe_0.67Zr_0.33, Fe_0.50Zr_0.50 and Fe_0.33Zr_0.67 reveal the formation of an amorphous phase. The growth of this phase and the crystallization of the intermetallic compound FeZr₃ for the rich zirconium sample are discussed.     

Structural characterization and ferromagnetic behavior of Fe-doped TiO2 powder by high-energy ball milling

Fe-doped TiO₂ powder was prepared by high-energy ball milling, using TiO₂ Degussa P-25 and α-Fe powders as the starting materials. The structure and magnetic properties of the Fe-doped TiO₂ powder were studied by X-ray diffraction, ⁵⁷Fe Mossbauer spectroscopy and vibrating sample magnetometer. The Reitveld refinement of XRD revealed that ball milling not only triggered incorporation of Fe in TiO₂ lattice but also induced the phase transformation from anatase to rutile in TiO₂ and consequently the milled Fe-doped TiO₂ powder contained only rutile.⁵⁷Fe Mössbauer effect measure showed that Fe atoms existed in Fe²⁺ and Fe³⁺ state, which were assigned to the solid solution Fe_xTi_1−xO₂. The magnetization measurements indicated that the milled Fe-doped TiO₂ powder was ferromagnetic above room temperature. The ferromagnetism in our milled Fe-doped TiO₂ powder seemingly does not come from Fe and iron oxides particles/clusters but from the Fe-doped TiO₂ powder matrices.     

Some features of magnetic domain structure reorganization during spin-reorientation phase transitions of the first and second order

On the basis of magnetic domain structure investigations in single crystals of R ₂Fe₁₄B, RFe₁₁Ti, RCo₅ intermetallic compounds (where R is a rare earth metal) in the temperature region 4.2–400 K, the features of domain structure transformation during spin reorientation transitions of the first and second order are analyzed.     

Hydrogen absorption in Zr(AlxB1−x)2 (BFe,Co) laves phase compounds

The hydrogen absorption capacity of the systems Zr(Al_xFe_1?x)₂ and Zr(Al_xCo_1?x)₂ (0? x ?1) was measured at hydrogen pressure of 70 atm and room temperature and at 40 atm and liquid nitrogen temperature. The two systems present very interesting and unexpected results.A dramatic rise in the hydrogen capacity occurs for small x values similar to previous results for the systems Zr(A_xB_1?x)₂ (A  V, Cr, Mn; B  Fe, Co; 0?x?1). The maximum hydrogen content in both systems is achieved for x ≈ $\text{2}\text{12}$ at 40 atm and 80 K. Further increase of the Al content leads, however, to a steep decrease in the hydrogen capacity. This general behaviour is well described by a phenomenological model, recently proposed by us, and thus supporting the importance of short-range neighbouring effects for the hydrogen absorption capacity. The influence of Al on the hydrogen sorption properties in different intermetallic compounds is discussed.     

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.     

Electric field gradients in nanoparticles of HfAl2 and HfAl3 intermetallic compounds

Perturbed angular correlation (PAC) method was applied to study the electric field gradients in nanopowders of the HfAl₂ and HfAl₃ intermetallic compounds, obtained via mechanical alloying or after ball milling of the thermally alloyed compound. The influence of the ball milling procedure on the experimentally obtained hyperfine interaction parameters was determined. A strong dependence of the PAC pattern on the milling time was evidenced and attributed to the structural disorder. The thickness of the outer damaged part of the grains depends on the crystallographic structure of the milled material. In HfAl₃ sample the influence of the milling procedure on the phase transformation was observed.     

Hydrogen desorption in Zr3Fe H5.5

Hydrogen desorption during heat treatments of (crystalline) Zr₃FeH_5.5 was studied by Mössbauer spectroscopy (MS), X-ray (powder) diffraction (XRD) and thermal gravimetry (TG). In case of sufficiently slow heating rate all hydrogen effuses below 650°K and no phase segregation occurs. At higher temperatures retained hydrogen induce phase separation into Fe₂Zr (or more likely Fe₂ZrH_x) and zirconium hydride. The existence of a highly disordered f.c. tetragonal ternary hydride phase was also detected both by XRD (a_o=4.76 Å, c=4.96 Å) and MS .     

Comparison of ball milling of Fe/Cr powders and Fe-Cr crystalline alloy

Using the mechanical attrition technique (MA), we have prepared a Fe-Cr alloy starting with a mixture of elemental iron and chromium powders with a nominal composition of 28 at% of Fe and 72 at% of Cr. MA was also performed on solid solutions of Fe₂₈Cr₇₂ crystalline alloy. The Mössbauer effect of the mechanically alloyed powder from Cr and Fe metals has been compared with that from crystalline alloy.