Effect of hot deformation on texture and magnetic properties of Sm-Co and Pr-Co alloys

Nanocrystalline PrCo₅, SmCo₅ and Sm₂(Co,Fe,Mn)₁₇ alloys were subjected to a high-degree plastic deformation at 950 °C with the height reduction ranging from 70% to 95%. With increasing degree of deformation, the PrCo₅ and SmCo₅ magnets showed improvement of the deformation-induced [0 0 1] texture. The PrCo₅ alloys, known to develop a superior texture at the lower degrees of deformation, showed only modest improvement and their magnetic performance was undermined by a low coercivity. The SmCo₅ alloys had their texture markedly enhanced and, after height reduction by 94.5%, they exhibited a remanence of 8.6 kG, maximum energy product of 18 MGOe and an intrinsic coercivity of 22.8 kOe. No induced texture was found in the alloys based on the Sm₂Co₁₇ structure. The microstructures of the hot-deformed alloys were studied with a transmission electron microscopy, and possible mechanisms of the texture development in the RCo₅ alloys (R=Pr, Sm) are briefly discussed.     

Study of solid-state reactions in Sm(Co,Fe, Cu,Zr)z 2:17-type alloys by means of in situ electrical resistivity measurements

In the present work, solid-state reactions in Sm₂(Co, Fe, Cu, Zr)₁₇-type alloys have been investigated by means of in situ electrical resistivity measurements. Changes in the electrical resistivity of a Sm(Co_0.74Fe_0.1Cu_0.12Zr_0.04)_8.5 alloy after solid solution treatment at 1190 °C, quenching to room temperature, and during isothermal ageing at temperatures between 400 and 900 °C, have indicated microstructural/phase changes occurring at temperatures below those commonly used for the development of high coercivity in Sm(Co, Fe, Cu, Zr)_z-type materials. Subsequent crystallographic and magnetic transition measurements have shown a high degree of correlation with respect to the changes observed in the electrical resistivity during isothermal ageing.     

Structural,microstructural and magnetic properties of nanocomposite isotropic Sm(CobalFe0.1MyZr0.04B0.04)7.5 ribbons with M=Ni,Cu and y=0.09 and 0.12

In boron-substituted melt-spun Sm(Co,Fe,Cu,Zr)_7.5-type alloys a nanocomposite microstructure and high coercivities in both as-spun and short-time annealed ribbons can be obtained. In the present study three different compositions, namely Sm(Co_0.73Fe_0.1Cu_0.09Zr_0.04B_0.04)_7.5, Sm(Co_0.70Fe_0.1Cu_0.12Zr_0.04B_0.04)_7.5 and Sm(Co_0.70Fe_0.1Ni_0.12Zr_0.04B_0.04)_7.5 have been examined in order to investigate the influence of composition on the magnetic properties and the microstructure. Melt-spun ribbons have been obtained and annealing has been followed under argon atmosphere for 30–75 min at 600–870 °C. For the as-spun ribbons the TbCu₇-type of structure and fcc-Co as a secondary phase have been identified in the X-ray diffraction patterns. For the annealed ribbons above 700 °C the 1:7 phase transforms into 2:17 and 1:5 phases. The TEM studies have shown a homogeneous nanocrystalline microstructure with average grain size of 30–80 nm. Coercivity values of 15–27 kOe have been obtained from hysteresis loops traced in non-saturating fields. The coercivity decreases with temperature, but it is sufficiently large to maintain values higher than 5 kOe at 380 °C.     

Epitaxial growth of Co(0 0 0 1)hcp/Fe(1 1 0)bcc magnetic bi-layer films on SrTiO3(1 1 1) substrates

Co(0 0 0 1)_hcp/Fe(1 1 0)_bcc epitaxial magnetic bi-layer films were successfully prepared on SrTiO₃(1 1 1) substrates. The crystallographic properties of Co/Fe epitaxial magnetic bi-layer films were investigated. Fe(1 1 0)_bcc soft magnetic layer grew epitaxially on SrTiO₃(1 1 1) substrate with two type variants, Nishiyama–Wasserman and Kurdjumov–Sachs relationships. An hcp-Co single-crystal layer is obtained on Ru(0 0 0 1)_hcp interlayer, while hcp-Co layer formed on Au(1 1 1)_fcc or Ag(1 1 1)_fcc interlayer is strained and may involve fcc-Co phase. It has been shown possible to prepare Co/Fe epitaxial magnetic bi-layer films which can be usable for patterned media application.     

Structural and magnetic properties of self-assembled Sm-Co spherical aggregates

Self-assembled Sm-Co nanoparticles in the form of spherical aggregates (referred as nanospheres) with diameter ranging from 50 to 180 nm were achieved by means of polyol technique. The size distribution of the Sm-Co nanospheres can be regulated close to ∼100 nm by controlling the molar ratio of Sm:Co precursor. The spherical aggregates exhibited Sm₂Co₇ phase as a major constituent; while the aggregates obtained at higher Co concentration showed co-existence of Co-phase with Sm₂Co₇ phase. Upon annealing, the biphasic nature of nanospheres (Sm₂Co₇/Co) transformed into Sm₂Co₁₇ structure. By varying the Sm:Co precursor ratio from 1:5 to 1:9, the coercivity (H_c) and magnetization (M_s) values of the as-synthesized nanospheres can be tuned from 336 to 140 Oe and from 63.7 to 108 emu/g, respectively, and these values significantly improved after annealing. Maximum values of H_c (1050 Oe) at the Sm:Co molar ratio of 1:5 and M_s of 184.6 emu/g at the Sm:Co molar ratio of 1:9 were achieved in the annealed samples.     

Electromagnetic properties of samarium-substituted NiCuZn ferrite prepared by auto-combustion method

Ni_0.25Cu_0.2Zn_0.55Sm_xFe_2−xO₄ ferrite with x=0.00, 0.025, 0.05 and 0.075 compositions were synthesized through the nitrate-citrate auto-combustion method. These powders were calcined, compacted and sintered at 900 °C for 4 h. Effect of Sm substitution on phase composition, microstructure and relative density were studied. Permeability, magnetic loss and AC resistivity were measured in the frequency range of 1 kHz-10 MHz. Permeability and AC resistivity were found to increase and loss decreased with Sm substitution up to x=0.05. Saturation magnetization also increased up to that substitution limit. Observed variations in electromagnetic properties have been explained.     

Structure and magnetic properties of SmCoxTi0.4-1:7 ribbons

SmCo_xTi_0.4 (x=6.6, 7.1, 7.6, 8.1) ribbons have been prepared by melt spinning at a wheel speed of 42 m/s, followed by annealing at 750 °C for 2 h. Both as-spun and as-annealed ribbons possess the disordered TbCu7-type (1:7) phase even when the Sm/(Co,Ti) atomic ratio deviates from 1/7. The c/a ratio increases with increasing Co concentration x, but the unit cell volume decreases. The Curie temperatures show above 700 °C, increasing from 707 °C for x=6.6 to 782 °C for x=8.1. The saturation magnetizations increase almost linearly with increasing Co content. The observed magnetic hardening is believed to arise from the high magnetocrystalline anisotropy of the 1:7 phase and the fine nanograin structure. The intrinsic coercivity of 9797 Oe has been obtained in the melt-spun SmCo_7.1Ti_0.4 ribbons.     

Tailoring the structural and magnetic properties of sol-gel derived Sm-Co nanogranular films

In this study, we investigated the microstructure, phase evolution and magnetic properties of nanogranular films of Sm-Co compounds processed by the sol-gel method. By controlling the compositional ratio of Sm:Co precursor concentration, nanogranular films consisting of three distinct hard magnetic phases namely, Sm₂Co₇, SmCo₅ and Sm₂Co₁₇ with coercivity values of 1.78, 2.94 and 2.12 kOe, respectively, were obtained through this technique.     

Out-of-equilibrium Sm–Fe based phases

Structure and magnetic properties of nanocrystalline P6/mmm out-of-equilibrium precursors of hard magnetic R-3m Sm₂(Fe,M)₁₇C (M=Ga,Si,) and I4/mmm Sm(Fe,Co,Ti)₁₁ equilibrium phases, are presented. Their structure is explained with a model ground on the R_1???s T_5?+?2s formula (R=rare-earth, s=vacancy rate, T=transition metal) where s Sm atoms are statistically substituted by s transition metal pairs. The Rietveld analysis (RA) provides the stoichiometry of the precursors, 1:9 and 1:10, respectively precursor of 2:17 and 1:12 phases. The interpretation of the Mössbauer spectra of the 1:9 and 1:10 phases, is based on the correlation between δ and the Wigner–Seitz Cell volumes, calculated from the structural parameters. The δ behaviour of each crystallographic site versus Co content, defines the Co location while it confirms that of Si and Ga obtained by RA. Substitution occurs in 3 g site, whatever Co or M. The Sm(Fe,Co,Ti)₁₀ and Sm(Fe,M)₉C Curie temperature (T_c) are compared to those of the equilibrium phases, the effects of Fe substitution and C addition are discussed. The maximum μ ₀H_c is obtained for low M or Co content, for auto-coherent diffraction domain size ～30 nm. SmFe_8.75Ga_0.25C and SmFe_8.75Si_0.25C with T_c of 680 and 690 K, show respectively M_r and μ ₀H_c of 58 emu/g, 27 kOe and 95 emu/g, 15 kOe, values higher than those obtained for Sm₂(Fe,M)₁₇ carbides.     

Coercivity mechanism of Sm(Co, Cu)5

The mechanism of the high intrinsic coercivity of the Sm(Co_1−xCu_x)₅ (0≦x<1) system was studied by relating the coherency between the lattice constants of hexagonal Sm(Co, Cu)₅ and hcp Co to the coercive force. It was found analytically that the intrinsic coercive force reaches a maximum in the composition range from x=0.6 to 0.8, where the lattice mismatch approaches zero, so that there is a strong correlation between lattice matching and coercive force. When a Sm ion was located within a Sm(Co, Cu)₅ grain and in the outmost edge of the a and c planes of its grain surrounded or not surrounded by the coherent Co phase, the crystal field parameter at each Sm³⁺ site was calculated using a point charge model under the assumption that the Co and Cu atoms located in a grain and the hcp Co atoms situated at the interface uniformly have a charge of 3/5−. The results indicated that the Co phase precipitated coherently along the grain boundaries effectively enhances the magnetocrystalline anisotropy of Sm ions located in the outmost edges of the a and c planes of a Sm(Co, Cu)₅ grain.     

Texture development and magnetic properties of [ZrO2/CoPt]n/Ag nanocomposite films

The L1₀ CoPt films with (0 0 1) preferred orientation are achieved by fabricating on the glass substrates and post annealing at 600° C for 30 min. The preferred orientation of [ZrO₂/CoPt]_n/Ag films dependence of the Ag underlayer thickness, ZrO₂ and CoPt interlayer thickness is investigated. A large perpendicular magnetic anisotropy and a nearly perfect L1₀ CoPt (0 0 1) texture are obtained in the [ZrO₂ (3 nm)/CoPt (5 nm)]₃/Ag (10 nm) film. The existence of ZrO₂ plays an important role in reducing the intergranular interactions and in determining the size of CoPt grains. Magnetic reversal in textured CoPt films are close to a Stoner-Wolfarth rotation.     

Magnetocaloric effect in R2Fe17 (R=Sm,Gd, Tb,Dy, Er)

A series of R₂Fe₁₇ (R=Sm, Gd, Tb, Dy, Er) have been synthesized. The magnetocaloric effect (MCE) of these compounds has been investigated by means of magnetic measurements in the vicinity of their Curie temperature. The Curie temperature of Er₂Fe₁₇ is 294 K. The maximum magnetic entropy change of Er₂Fe₁₇ under 5 T magnetic field is ∼3.68 J/kg K. In the R₂Fe₁₇ (R=Sm, Gd, Tb, Dy, Er) system, the maximum magnetic entropy change under 1.5 T magnetic field is 1.72, 0.89, 1.32, 1.59, 1.68 J/kg K corresponding to their Curie temperature (400, 472, 415, 364, 294 K), respectively.     

Structure and magnetic properties of (Nd,Dy)16(Fe,Co)76−xTixB8 powders prepared by mechanical alloying

Nanocrystalline (Nd,Dy)₁₆(Fe,Co)_76−xTi_xB₈ magnets were prepared by mechanical alloying and respective heat treatment at 973–1073 K/30–60 min. An addition of 0.5 at % of Ti results in an increase of coercivity from 796 to 1115 kA m⁻¹. Partial substitution of Nd by Dy results in an additional increase of coercivity up to 1234 kA m⁻¹. Mössbauer investigations shows that for x?1 the (Nd,Dy)₁₆(Fe,Co)_76−xTi_xB₈ powders are single phase. For higher Ti contents (x>1) the mechanically alloyed powders heat treated at 973 K are no more single phase, and the coercivity decreases due to the presence of an amorphous phase. A heat treatment at a higher temperature (1073 K) for longer time (1 h) results in the full recrystallisation of powders. The mean hyperfine field of the Nd₂Fe₁₄B phase decreases for titanium contents of 0?x?1, and remains constant for x>1. This indicates that the Ti content in the Nd₂Fe₁₄B phase reaches its maximum value.     

Solid-state synthesis and phase transformations in Ni/Fe films: Structural and magnetic studies

We have used X-ray diffraction, volume magnetocrystalline anisotropy constant and resistance measurements to study solid-state synthesis in Ni(0 0 1)/Fe(0 0 1), Ni/Fe(0 0 1) and Ni/Fe thin films with the atomic ratio between Fe and Ni of 1:1 (1Fe:1Ni), and 3:1 (3Fe:1Ni). We have found that the formation of Ni₃Fe and NiFe phases in the 1Fe:1Ni films takes place at temperatures ∼620 and ∼720 K, correspondingly. In the case of the 3Fe:1Ni films the solid-state synthesis starts with Ni₃Fe and NiFe phase formation at the same temperatures as for the 1Fe:1Ni films. The increasing of annealing temperature above 820 K leads to the nucleation of a paramagnetic γ_par phase at the FeNi/Fe interface. The final products of solid-state synthesis in the Ni(0 0 1)/Fe(0 0 1) thin films are crystallites which consist of the epitaxially intergrown NiFe and γ_par phases according to the [1 0 0](0 0 1)NiFe||[1 0 0](0 0 1)γ_par orientation relationship. The crystalline perfection and epitaxial growth of the (NiFe+γ_par) crystallites on the MgO(0 0 1) surface allow to distinguish (0 0 2)γ_par and (0 0 2)NiFe X-ray peaks (the cell parameters are: a(γ_par)=0.3600±0.0005 nm and a(NiFe)=0.3578±0.0005 nm, correspondingly). At low temperatures the paramagnetic γ_par phase undergoes the martensite _γpar→α^′${\gamma }_{\mathrm{par}}\to {\alpha }^{\prime }$ phase transition which can be hindered by thermal and epitaxial strains and epitaxial clamping with a MgO substrate. On the basis of the studies of the thin-film solid-state synthesis we predict the existence of two novel structural phase transformations at the temperatures of about 720 and 820 K for alloys of the invar region of the Fe–Ni system.     

2:17-type SmCo magnets prepared by powder injection molding using a water-based binder

2:17-type SmCo permanent magnets by powder injection molding using a water-based binder have been studied. The water-based binder is methylcellulose solution, which consists of deionized water and methylcellulose. When the solution concentration is 0.5 wt%, the carbon content of the sintered magnets is below 0.1 wt% and the magnets have better magnetic properties. The magnetic properties and density of the sintered magnets can be increased through pre-sintering in vacuum (10⁻³ Pa) at 1200 °C. However, the Sm content of the magnets loses obviously in pre-sintering for a long period. The appropriate pre-sintering duration is 20–40 min. The magnetic properties of the magnets are: Br=0.97 T, H_cj=871 kA/m, BH_max=157 kJ/m³. The structure of the magnet consists of the matrix phases (2:17 phases) and the precipitate phases (1:5 phases).     

Magnetic and structural studies of the double perovskites Ba2REMoO6

A magnetic, electronic and structural study of the double perovskites Ba₂REMoO₆ (RE=Sm, Eu, Gd, Dy) has been performed. All materials crystallise in the cubic symmetry space group and the cell volume decreases as RE varies from Sm to Dy in accordance with Vegard's law. An antiferromagnetic transition is observed below T_N=130 and 112 K for RE=Sm and Eu, respectively. The Néel temperatures of these ordered rare earth molybdenum double perovskites are much higher than previously observed in double perovskites containing Eu or Sm and a 4d or 5d transition metal arranged in an ordered rock salt configuration. The high Néel temperatures arise due to a strong superexchange magnetic interaction via the Mo-O-RE-O-Mo pathway. All of the phases are electronically insulating and there is no evidence of magnetoresistance at any temperature.     

Structural and magnetic properties of evaporated Fe thin films on Si(1 1 1), Si(1 0 0) and glass substrates

We present experimental results on the structural and magnetic properties of series of Fe thin films evaporated onto Si(1 1 1), Si(1 0 0) and glass substrates. The Fe thickness, t, ranges from 6 to110 nm. X-ray diffraction (XRD) and atomic force microscopy (AFM) have been used to study the structure and surface morphology of these films. The magnetic properties were investigated by means of the Brillouin light scattering (BLS) and magnetic force microscopy (MFM) techniques. The Fe films grow with (1 1 0) texture; as t increases, this (1 1 0) texture becomes weaker for Fe/Si, while for Fe/glass, the texture changes from (1 1 0) to (2 1 1). Grains are larger in Fe/Si than in Fe/glass. The effective magnetization, 4πM_eff, inferred from BLS was found to be lower than the 4πM_S bulk value. Stress induced anisotropy might be in part responsible for this difference. MFM images reveal stripe domain structure for the 110 nm thick Fe/Si(1 0 0) only.     

Ion dependence of magnetic anisotropy in MFe2O4 (MFe,Co, Mn) nanoparticles synthesized by high-temperature reaction

The influence of different M²⁺ cations on the effective magnetic anisotropy of systems composed of MFe₂O₄ (M=Fe, Co and Mn) nanoparticles was investigated. Samples were prepared by the high-temperature (538 K) solution phase reaction of Fe (acac)₃, Co (acac)₂ and Mn (acac)₂ with 1,2 octanodiol in the presence of oleic acid and oleylamine. The final particles are coated by an organic layer of oleic acid that prevents agglomeration. Transmission electron microscopy (TEM) images show that particles present near spherical form and a narrow grain size distribution, with mean diameters in the range of 4.5–7.6 nm. Powder samples were analyzed by ac susceptibility and Mössbauer measurements, and K_eff for all samples was evaluated using both techniques, showing a strong dependence on the nature of the divalent cation.     

Magnetic anomalies in single crystalline ErPd2Si2

Considering certain interesting features in the previously reported ¹⁶⁶Er Mössbauer effect, and neutron diffraction data on the polycrystalline form of ErPd₂Si₂ crystallizing in the ThCr₂Si₂-type tetragonal structure, we have carried out magnetic measurements (1.8–300 K) on the single crystalline form of this compound. We observe significant anisotropy in the absolute values of magnetization (indicating that the easy axis is c-axis) as well as in features due to magnetic ordering in the plot of magnetic susceptibility χ versus temperature T at low temperatures. The χ(T) data reveal that there is a pseudo-low-dimensional magnetic order setting in at 4.8 K, with a three-dimensional antiferromagnetic order setting in at a lower temperature (3.8 K). A new finding in the χ(T) data is that, for H∥〈1 1 0〉 but not for H∥〈0 0 1〉, there is a broad shoulder in the range 8–20 K, indicative of the existence of magnetic correlations above 5 K as well, which could be related to the previously reported slow-relaxation-dominated Mössbauer spectra. Interestingly, the temperature coefficient of electrical resistivity is found to be isotropic; no feature due to magnetic ordering could be detected in the electrical resistivity data at low temperatures, which is attributed to magnetic Brillioun-zone boundary gap effects. The results reveal the complex nature of magnetism of this compound.     

Synthesis and magnetic characterization of cobalt-substituted ferrite (CoxFe3−xO4) nanoparticles

Cobalt-substituted ferrite nanoparticles were synthesized with a narrow size distribution using reverse micelles formed in the system water/AOT/isooctane. Fe:Co ratios of 3:1, 4:1, and 5:1 were used in the synthesis, obtaining cobalt-substituted ferrites (Co_xFe_3−xO₄) and some indication of γ-Fe₃O₄ when 4:1 and 5:1 Fe:Co ratios were used. Inductively coupled plasma mass spectroscopy (ICP-MS) verified the presence of cobalt in all samples. Fourier transform infrared (FTIR) showed bands at ∼560 and ∼400 cm⁻¹, characteristic of the metal–oxygen bond in ferrites. Transmission electron microscopy showed that the number median diameter of the particles was ∼3 nm with a geometric deviation of ∼0.2. X-ray diffraction (XRD) confirmed the inverse spinel structure typical of ferrites with a lattice parameter of a=8.388 Å for Co_0.61Fe_0.39O₄, which is near that of CoFe₂O₄ (a=8.394 Å). Magnetic properties were determined using a superconducting quantum interference device (SQUID). Coercivities higher than 8 kOe were observed at 5 K, whereas at 300 K the particles showed superparamagnetic behavior. The anisotropy constant was determined based on the Debye model for a magnetic dipole in an oscillating field and an expression relating χ′ and the temperature of the in-phase susceptibility peak. Anisotropy constant values in the order of ∼10⁶ erg/cm³ were determined using the Debye model, whereas anisotropy constants in the order of ∼10⁷ erg/cm³ were calculated assuming Ωτ=1 at the temperature peak of the in-phase component of the susceptibility curve as commonly done in the literature. Our analysis demonstrates that the assumption Ωτ=1 at the temperature peak of χ′ is rigorously incorrect.