Diffusion of Fe,Co, Nd,and Dy in R2(Fe1−xCox)14B where R=Nd or Dy

Transition metal and rare earth diffusion coefficients at 1323 K in Dy_2−yNd_y(Fe_1−xCo_x)₁₄B were determined by field emission energy dispersive spectroscopy compositional analysis of diffusion couple specimens. Various arrangements of component materials and temperatures were examined in order to understand the mechanisms affecting diffusion of the components and to predict the stability of functionally graded microstructures consisting of a dysprosium-rich (Dy_2−yNd_y(Fe_1−xCo_x)₁₄B) outer layer and a neodymium-rich (Nd₂(Fe_1−xCo_x)₁₄B) interior. Estimates of the mutual interdiffusion coefficients of Dy, Nd, Fe, and Co in this system were obtained from the preparation of arc melted and annealed polycrystalline specimens, assuming that the diffusion coefficients were independent of concentration (Grube solution). Fifteen diffusion couples were prepared and heat treated at 1323 K for various times in order to provide data for calculation of the diffusion coefficients. The results indicate that the diffusion coefficients of Fe and Co (D_Fe=3.28×10⁻¹⁰ cm²/s and D_Co=7.63×10⁻¹⁰ cm²/s) were significantly higher at 1323 K in this system than those for Dy and Nd (D_Nd=2.3×10⁻¹² cm²/s and D_Dy=2.9×10⁻¹² cm²/s).     

Phase relations of the (Pr1−xSmx)2Fe14B system

The phase relations in the (Pr_1?xSm_x)₂Fe₁₄B system in a whole concentration range have been studied by means of X-ray powder diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy (SEM) equipped with energy-dispersive X-ray spectroscopy (EDS). The XRD patterns of the (Pr_1?xSm_x)₂Fe₁₄B samples have been refined by Rietveld method. These results reveal that all the alloys (Pr_1?xSm_x)₂Fe₁₄B are similar to the end member of the investigated system Pr₂Fe₁₄B with tetragonal structure (space group P4₂/mnm). The continuous solid solutions were formed in this system. The normalized lattice parameters and unit cell volumes of (Pr_1?xSm_x)₂Fe₁₄B solid solutions decrease linearly with x ranging from 0 to 1.0. The DTA measurements show that the peritectic temperature of (Pr_1?xSm_x)₂Fe₁₄B increases with increasing Sm content and no metastable phases are detected. Based on the DTA data, SEM–EDS and XRD results, the vertical section of Pr₂Fe₁₄B–Sm₂Fe₁₄B in the Pr–Sm–Fe–B system has been constructed.     

Observations of multi-phase microstructures in R2(Fe1−xCox)14B where R=Nd or Dy

Multi-phase microstructures were observed in the psuedo-quaternary phase field of the 2–14–1 magnet materials Nd₂Fe₁₄B, Nd₂Co₁₄B, Dy₂Fe₁₄B, and Dy₂Co₁₄B. At equilibrium, (Nd_1−yDy_y)₂(Fe_1−xCo_x)₁₄B had heretofore been widely assumed to be single phase where 1>x>0 and 1>y>0. In this study, three-phase microstructures were observed in (Nd_1−yDy_y)₂(Fe_1−xCo_x)₁₄B when x>0.3 and y>0.5. The Curie temperatures and peritectic decomposition temperatures for Nd₂(Fe_1−xCo_x)₁₄B are reported for several values of x in the range 1>x>0.     

Mössbauer study of the intermetallic compound Nd2Fe14B. II. Temperature dependence and spin reorientation

The ⁵⁷Fe Mössbauer effects of Nd₂Fe₁₄B were measured in a temperature range of 4.2−300 K. Below the spin reorientation transition temperature T_sc = 148 K, the spectra were satisfactorily analyzed with twelve Zeeman sextuplets due to splitting of six crystallographic Fe-sites into twelve non-equivalent sites. It was shown that the magnetic moments of the Fe and the Nd atoms are non-collinearly coupled in the magnetic structure with canted moments below T_sc. The directions of the moments at 4.2 K are inclined at 27° for Fe and at 58° for Nd from the c-axis to the [110] direction. The average moments are 2.27μ_B for Fe and 3.3μ_B for Nd at 4.2 K. The increase of the average hyperfine field with decreasing temperature is suppressed below T_sc, and its value at 4.2 K is reduced by 1% from the value of 337 kOe which is observed in Y₂Fe₁₄B and also estimated for Nd₂Fe₁₄B by extrapolating the values above T_sc. On the other hand, the Nd moment increases abruptly around T_sc as the temperature decreases. The directions of the principal axes of electric field gradients on the six distinct Fe-sites were also obtained. The anomalous temperature dependence of quadrupole splittings and isomer shifts was observed around T_sc. They were discussed in a framework of the changes in the band structure and the lattice parameters incidental to the spin reorientation transition.     

Temperature variation of the spin reorientation in Er2−xDyxFe14B alloys

The competition between the uniaxial magnetic anisotropy of the iron sublattice and the basal anisotropy of the rare earth sublattice in the R₂Fe₁₄B alloys, occuring for the rare earths with a positive Steven's factor (a_j> 0), leads to spin reorientation at 316 K for the Er₂Fe₁₄B compound. We have succeeded, by making a series of pseudoternaries of the type Er_2−xDy_xFe₁₄b, to establish a correlation between the spin reorientation temperature and the quantity x. Mossbauer spectra of aligned powders show a smooth decrease of the spin reorientation temperature for values of x up to 1, while for larger values spin reorientation is absent.     

Magnetic properties of U (Fe x Al1−x )2 and U(Fe y Ni1−y )2 compounds

The results of magnetic measurements and ferromagnetic resonance studies performed on U(Fe _x Al_1–x )₂ and U(Fe _y Ni_1–y )₂ compounds over a large temperature range are reported. The saturation magnetization decreases nearly linearly when substituting Fe by Al or Ni. In the composition range x<0.84 and y<0.81, the compounds are Pauli paramagnets, except in the region with y0.10. For UNi₂ two types of magnetic behaviours are shown. This compound can be both a ferromagnet withT _c =23.5 K and a Pauli paramagnet, depending on the crystal structure. Above the Curie temperatures, the reciprocal susceptibility for the compounds with x>0.84 and y>0.81 obeys a temperature dependence of the formX=X _o+C(T-) ^–1. The effective iron moments decrease when substituting iron by nickel or aluminium. The ferromagnetic resonance measurements show that theg values are not composition-dependent. A linear variation of the mean iron magnetization with the exchange field is observed. Finally, the magnetic behaviour of iron in these compounds is analysed.     

Calculation of the electronic structure and hyperfine fields for Fe1 − x Co x B and (Fe1 − x Co x )2B compounds by the Korringa-Kohn-Rostoker method

The magnetic properties of Fe_{1 ? x} Co _x B and (Fe_{1 ? x} Co _x )₂B disordered compounds were investigated using first-principles calculations of the electronic structure in the framework of the density functional theory with the Korringa-Kohn-Rostoker method. The concentration dependences of the magnetic moments and the electron density were calculated for the Fe_{1 ? x} Co _x B solid solutions. The results obtained were used to analyze in detail and to interpret the transition from a magnetic phase to a nonmagnetic phase, which was previously revealed from the experiments in the compounds under investigation. The performed analysis of the calculated hyperfine fields induced by the electronic shells at the iron and cobalt atoms in the (Fe_{1 ? x} Co _x )₂B borides made it possible to explain the experimentally observed magnetic anisotropy.     

Magnetic anisotropy in thin films of metallic glasses Fe1−xBx alloys

Noninduced uniaxial magnetic anisotropy in Fe_1−xB_x thin films of metallic glasses was studied for 26⩽x⩽32. The samples were obtained by rf sputtering technique. Thickness and compositional dependence of uniaxial magnetic anisotropy was determined for films with thickness d⩽120 nm. The existence of the uniaxial magnetic anisotropy can be explained roughly by a directional alignment of free volume and directional order of atomic pairs in the vicinity of the free volume.     

Three-and two-dimensional calculations for the interface anisotropy dependence of magnetic properties of exchange-spring Nd2Fe(14)B/α-Fe multilayers with out-of-plane easy axes

Hysteresis loops,energy products and magnetic moment distributions of perpendicularly oriented Nd2Fe(14)B/α-Fe exchange-spring multilayers are studied systematically based on both three-dimensional(3D)and one-dimensional(1D)micromagnetic methods,focused on the influence of the interface anisotropy.The calculated results are carefully compared with each other.The interface anisotropy effect is very palpable on the nucleation,pinning and coercive fields when the soft layer is very thin.However,as the soft layer thickness increases,the pinning and coercive fields are almost unchanged with the increment of interface anisotropy though the nucleation field still monotonically rises.Negative interface anisotropy decreases the maximum energy products and increases slightly the angles between the magnetization and applied field.The magnetic moment distributions in the thickness direction at various applied fields demonstrate a progress of three-step magnetic reversal,i.e.,nucleation,evolution and irreversible motion of the domain wall.The above results calculated by two models are in good agreement with each other.Moreover,the in-plane magnetic moment orientations based on two models are different.The 3D calculation shows a progress of generation and disappearance of vortex state,however,the magnetization orientations within the film plane calculated by the 1D model are coherent.Simulation results suggest that negative interface anisotropy is necessarily avoided experimentally.     

取向Pr2Fe14B与Nd2Fe14B多晶磁化曲线的计算

基于单离子晶场模型 ,提出了计算稀土 Fe(Co)金属间化合物取向多晶样品磁化曲线的方法 .用此方法计算了取向Pr2 Fe14 B和Nd2 Fe14 B多晶的高场磁化曲线 ,计算中使用了拟合化合物单晶磁化曲线得到的交换场与晶场参数 .计算曲线与实验曲线相符合 .     

Effects of underlayer materials and substrate temperatures on the structural and magnetic properties of Nd2Fe14B films

Thin films of Nd_2Fe_{14}B were fabricated on heated glass substrates by dc magnetron sputtering. Different material underlayers (Ta, Mo, or W) were used to examine the underlayer influence on the structural and magnetic properties of the NdFeB films. Deposited on a Ta buffer layer at 420℃, the 300 nm thick NdFeB films were shown to be isotropic. But when the substrate temperature T_s was elevated to 520℃, the Nd_2Fe_{14}B crystallites of (00l) plane were epitaxially grown on Ta (110) underlayer. In contrast, Mo (110) buffer layer could not induce any preferential orientation in NdFeB film irrespective of the substrate temperature or film thickness. The W buffer layer was found to be most effective for the nucleation of Nd_2Fe_{14}B crystallites with c-axis alignment perpendicular to the film plane when T_s<490℃. But at T_s=490℃ the magnetic layer became isotropic. The maximum coercivity obtained was about 995 kA/m for the 100nm film deposited on W underlayer at 490℃. These variations were tentatively explained in terms of the lattice misfit between the underlayer and the magnetic layer, combined with the considerations of underlayer morphologies.     

Structure and magnetism of the R2Fe14−xCoxB ferrimagnetic systems (R = Dy and Er)

R₂Fe_14−xCo_xB ferrimagnetic systems (R = Dy and Er) have been synthesized and studied by X-ray and magnetometry methods to determine the lattice parameters, Curie temperatures, saturation magnetizations, anisotropy fields and spin-reorientation temperatures. It has been established that the single phase materials, exhibiting a tetragonal crystal structure, can be formed in the Dy-based system only for x ⩽ 8, while in the Er-based system only for x ⩽ 5. An average increase of the Curie temperature of 58 K per one substituted Fe atom by Co is observed for both systems (x ⩽ 5). A characteristic maximum in composition dependence of the saturation magnetizations at 295 K is found for x ≃ 2, although this is less pronounced than in light rare earth-based Co-substituted systems. The composition dependencies of the anisotropy fields for the Dy-based system at 77 and 295 K show distinct maxima for low Co concentrations and a sharp decrease for higher Co content. The spin-reorientation temperature for the Er-based system is shifted towards higher temperatures by the Co substitution. A brief comparison between ferro- and ferrimagnetic R₂Fe_14−xCo_xB systems is included.     

Effect of the substitution of Pr for Nd on microstructure and magnetic properties of nanocomposite Nd2Fe14B/α-Fe magnets

Microstructure and magnetic properties of melt-spun nanocomposite magnets with nominal compositions of (Nd_1−xPr_x)₉Fe₈₆B₅ (x=0–1) were investigated. Substitution of Nd by Pr could significantly improve the hard magnetic properties of the nanocomposite magnets; the intrinsic coercivity (_iH_c) and the maximum magnetic energy product ((BH)_max) increase from 414 kA/m and 124 kJ/m³ for x=0 to 493 kA/m and 152 kJ/m³ for x=0.6, respectively. Further substituting Nd by Pr (x>0.6) strongly weakens exchange-coupling interaction between magnetically hard and soft phases.     

Mössbauer study of amorphous (Fe1−x Ga x )84B16

Using the⁵⁷Fe Mössbauer effect the influence of the Ga content in amorphous (Fe_1?x Ga _x )₈₄B₁₆ on the average hyperfine fields \(\bar H\) and isomer shift has been studied. For the sample (Fe_0.98Ga_0.02)₈₄B₁₆ the \(\bar H\) , as well as the recoilless fraction,f _a were measured as functions of temperature ranging from 12 K to 300 K. The experimental results show a linear correlation between Inf _a and δ, and well as between δ andx. In the temperature range \(\bar H(T)\) can be described by the Brillouin function and the second-order Doppler shift is appreciable. The characteristic temperature for such an amorphous alloy is 372 K. the effective vibrating massM _eff=79 a.u.     

X-ray photoelectron spectroscopy analysis of (Ln1−xSrx)CoO3−δ (Ln: Pr,Nd and Sm)

The chemical states of the surface of (Ln_0.5Sr_0.5)CoO_3?δ (Ln (lanthanides) = Pr, Nd and Sm) used for cathode materials of intermediate temperature operating solid oxide fuel cells (IT-SOFCs) were investigated by X-ray photoelectron spectroscopy (XPS). Oxygen peaks comprised of lower binding energy (LBE) and higher binding energy (HBE) peaks from (Ln_0.5Sr_0.5)CoO_3?δ and Pr_0.3Sr_0.7CoO_3?δ (PSC37) showed that some merged oxygen peak behavior is a function of the Sr and lanthanide concentrations. By investigating the oxygen peaks, it was determined that more oxygen vacancies were generated on the surface of the cathodes when the lanthanides and Sr were substituted into perovskite oxides. When comparing the binding energies (BEs) of PSC37 with Pr_0.5Sr_0.5CoO_3?δ (PSC55), the LBE and HBE of the Sr peaks both increased when Sr was substituted at the A-site of a perovskite. Surface analysis of the Co peak on the surface of the cathode materials showed that the Co exists mainly as Co³⁺ and partially oxidized to Co⁴⁺ on the cathode materials. The partial existence of Co⁴⁺ can provide some polaron hopping providing electronic conduction for the solid oxide fuel cell.     

Texture in NdFeB magnets analysed on the basis of the determination of Nd2Fe14B single crystals easy growth axis

We have shown by X-ray analysis and magnetic measurements, that the easy growth axis of Nd₂Fe₁₄B crystals corresponds to the “a” axis of the tetragonal structure while the easy magnetization axis is the “c” axis at temperatures above 135K. This correlation allows to understand some interesting features in NdFeB magnets:

• &#x02022;-anisotropic contraction during sintering in magnets obtained by classical powder metallurgy,
• &#x02022;-orientation mechanism during hot pressing (“die upset”) of magnets based on melt spun ribons.

     

Magnetic properties of (Nd,Pr)–Fe–B nanocomposite over quenched and annealed ribbons

The base alloys of nominal composition (Nd_0.75Pr_0.25)_yFe_balanceB_x (y=10−9.2 and x=6−19.2) were chosen to study the influence of RE/B ratio, smaller than stochiometric composition on magnetic properties of over quenched and annealed ribbons. From X-ray diffraction analysis of these ribbons, the α-Fe and Fe₃B phases were observed along with (Nd,Pr)₂Fe₁₄B major phase. The average grain size was calculated using these patterns as: 35 nm for α-Fe, 45 nm for (Nd,Pr)₂Fe₁₄B and 22 nm for Fe₃B particles. TEM analysis also supported the nano distribution of the above phases. These X-ray graphs support the idea of exchange coupling between hard and soft phases responsible for the observed magnetic properties. In these ribbons the saturation magnetization J_s and remnant magnetization J_r increases from 1.19 T to 1.66 T and from 0.65 T to 0.91 T, respectively as RE/B ratio increases. The increase in J_s and J_r may be attributed to the presence of exchange coupling between these phases. The corresponding coercivity _jH_c decreases from 673.33 to 271.33 k Am⁻¹. The maximum energy product (BH)_max initially increases from 72.42 kJ m⁻³to 109.85 kJ m⁻³ up to RE/B≈1 and then decreases to 58.5 kJ m⁻³, depending on the shape of second quadrant B–H loop. The coercivity mechanism observed from initial hysteresis curve was considered to be nucleation of domain wall.     

Optical anisotropy of the (100) surfaces in AlxGa1−x As ternary compounds

The reflectance anisotropy spectra of the clean (100) surfaces of the Al_xGa_1?x As ternary compounds at aluminum concentrations 0≤x≤0.5 have been measured and thoroughly studied. In the spectral range from 1.6 to 3.5 eV, the signal caused by the optical transitions in the arsenic dimers dominates in the spectra of the clean arsenic-terminated GaAs surfaces. For the ternary compounds, an increase in the aluminum concentration brings about the broadening of this signal and its shift toward the low-energy range. This is explained by the appearance of additional signals associated with the optical transitions in the nonequivalent arsenic dimers, in which a part of the Ga atoms in the bulklike bonds is replaced by the Al atoms. An increase in the number of the substituted gallium atoms leads to a decrease in the energy of optical transition in the dimer. The fundamental optical transition energies are determined for the nonequivalent dimers.     

Spin−wave resonance as a way of studying the constant of surface anisotropy,using films of Fe–Ni alloy as an example

The effect the thickness and concentration composition of a ferromagnetic thin film have on surface anisotropy constant K _S is investigated. Spin–wave resonance is chosen as a way of detecting and measuring the K _S value. Fe–Ni thin films are synthesized via chemical deposition. Dependences of K _S on the content of Ni in the alloy and a film’s thickness are established.     

Mössbauer Study of the Fe3B/Nd2Fe14B Nanocomposite Magnet by the Addition of Co

The addition of Co to Nd₄Fe_77.5–x Co _x Hf_0.5Ga_0.5B_18.5 (0x5) was found to enhance the magnetic properties of Fe₃B/Nd₂Fe₁₄B nanocomposite magnets. The enhancement resulted from the fact that Co tends to retard the formation of Fe₃B from the amorphous matrix but to accelerate that of Nd₂Fe₁₄B. The decreased interval between the crystallization temperature of Fe₃B and Nd₂Fe₁₄B led to a uniform grain size distribution of both phases during the annealing treatment. The additive Co was confirmed to partition mainly to Nd₂Fe₁₄B crystals rather than to Fe₃B which was traced by XRD and Mössbauer spectroscopy as well. About 72 vol.% of Fe₃B, 27 vol.% of Nd₂Fe₁₄B, and a small amount of Fe around 1 vol.%, respectively, were found to form. However, the volume fraction of each phase did not vary by the addition of Co up to 5 at.%.