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.     

The influence of pH and bath composition on the properties of Fe-Co alloy film electrodeposition

Fe-Co films were electrodeposited on ITO glass substrates from the electrolytes with different molar ratio of Co²⁺/Fe²⁺ and different pH values (2.1, 2.9, 3.7, and 4.3) at 25 °C. The properties of Fe-Co alloy films depend on both Co²⁺ and Fe²⁺ concentrations in electrolyte and pH values was studied. The content of Co increases from 40% to 85% as the mole ratio of CoSO₄/FeSO₄ increasing from 0.50/0.50 to 0.90/0.10 in electrolyte and slightly decreases from 77% to 63% as the pH values increasing from 2.1 to 4.3. The X-ray diffraction analysis reveals that the structures of the films strongly depend on the Co content in the binary films. The surface morphologies of the films are influenced by the combined action of composition and phase structure. The saturation magnetization reaches a maximum value of 2974.03 emu/cm³ and coercivity reaches a minimum value of 42.72 Oe of the Fe_0.30Co_0.70. The saturation magnetization reaches a maximum values of 2974.03 emu/cm³ and coercivity reaches a minimum values of 42.72 Oe of the Fe_0.30Co_0.70 at pH = 2.9.     

Magnetic properties of cobalt substituted M-type barium hexaferrite prepared by co-precipitation

The co-precipitation and solid state methods were used in the synthesis of barium hexaferrite (BaM). Phase pure BaM was obtained with 1, 2, 3, 5, 10, 15, 20 and 30 wt% cobalt oxide (Co₃O₄). The addition of Co^2+/3+ ions to the BaM increased the permeability and magnetic loss tangent to a value of 3.5 at 5% and reduced to 1 at 30% doping. With increased Co doping, M_s was reduced from 87-58 emu/g, M_r increased from 11 to 40 emu/g with 3–5 wt% Co and 9 emu/g for 30% doping. H_c sharply increased from 540 to 2200 Oe with a reduction to 280 Oe at 10 K with increasing temperature to 300 K. T_c increased from 740 to 750 K for 30% Co doping. DTA–TGA studies of green body showed decarboxilation to occur at around 825 °C and the transformation of residual Co₃O₄ to Co₂O₃ at around 577 °C. The XRD data confirmed the Co ions substituting into Fe sites until a 10–15% doping level where the structure altered to W-type hexaferrite. The densities of the compounds varied with doping to a maximum of 4.45 g/cm³.     

Preparation and magnetic properties of anisotropic (Sm,Pr)Co5/Co composite particles

Anisotropic (Sm,Pr)Co₅/Co nanocomposite particles have been fabricated by chemical coating the 2 h ball milled (Sm,Pr)Co₅ flakes with Co nanoparticles. The Co nanoparticles were synthesized with mean particle sizes in the range of 20-50 nm. The nanocomposite particles present [0 0 1] out-of-plane texture and improved magnetic properties, e.g., an enhanced remanent magnetization of 72 emu/g for (Sm,Pr)Co₅/Co and 66 emu/g for (Sm,Pr)Co₅. In addition, by using the 8 h ball milled powders (much smaller than the 2 h ball milled powders) as the starting materials, Co nanoparticles can also be successfully coated on the surface of the flakes. A plausible mechanism for the formation of Co nanoparticles on the surface of (Sm,Pr)Co₅ flakes is discussed.     

Effect of annealing on phase composition,structural and magnetic properties of Sm-Co based nanomagnetic material synthesized by sol-gel process

Sm-Co based nanomagnetic material was synthesized by means of a Pechini-type sol-gel process. In this method, a suitable gel-precursor was prepared using respective metal salts and complexing agent such as citric acid. The gel-precursor was dried at 300 °C and then subjected to various reductive annealing temperatures: 350, 500 and 600 °C. The nanopowders so obtained were characterized for their structure, phase composition and magnetic properties. FT-IR studies on the gel-precursor showed the binding of metal cations with the citrate molecules in the form of metal-citrate complex. The gel-precursor, which was annealed at 350 °C showed the presence of both meta-stable cobalt carbide (Co₂C, Co₃C) and Co₃O₄ phases; while the sample annealed at 500 °C indicated the sign of SmCo₅ phase. Upon increasing the reductive annealing temperature to 600 °C, crystalline phase such as fcc-Co and Sm₂C₃ were formed prominently. FE-SEM analysis revealed the change in sample morphology from spherical to oblate spheres upon increasing the annealing temperature. VSM measurements demonstrated ferromagnetic nature at room temperature for all the nanopowders obtained irrespective of their after reductive annealing temperature.     

Soft magnetic properties of FeCo films with Co underlayer

Bilayered Fe₆₅Co₃₅ (=FeCo)/Co films were prepared by facing targets sputtering with 4πM_s∼24 kg. The soft magnetic properties of FeCo films were induced by a Co underlayer. H_c decreased rapidly when the Co underlayer was 2 nm or more. The films showed well-defined in-plane uniaxial anisotropy with the typical values of H_ce=10 Oe and H_ch=3 Oe, respectively. High frequency characteristics of the films show the films can work at 0.8 GHz with real permeability as high as 250.     

Deformation-induced texture in nanocrystalline 2:17, 1:5 and 2:7 Sm-Co magnets

The effect of crystal structures on texture induced by hot plastic deformation was studied for Sm-Co, Sm-Zr-Co, Sm-Zr-Co-Fe and Sm-Co-Fe-Mn nanocrystalline alloys with 9-22 at% Sm. Nanocrystalline precursors were obtained via high-energy ball milling and subsequent hot consolidation; deformation was carried out at 800-1150 °C. The analysis of X-ray diffraction and magnetic measurements showed that the degree of the axial [0 0 1] texture after deformation was negligible for the ordered 2:17 structure, but became increasingly noticeable for the disordered 2:17 (“1:7”), 1:5 and 2:7 structures. Because of interplay of several factors including the [0 0 1] texture, saturation magnetization and magnetocrystalline anisotropy, there was no universal trend in the hard magnetic properties with the Sm content. Optimum compositions for the maximum energy product varied from Sm₁₁(Co, Fe, Mn)₈₉ in the Sm-Co-Fe-Mn series to Sm₁₁Zr₂(Co, Fe)₈₇ in the Sm-Zr-Co-Fe series to Sm₁₇(Co, Fe)₈₃ in the Sm-Co-(Fe) series. Iron substitution for cobalt strongly suppresses the 1:5 structure, whereas the Fe-free magnets based on the SmCo₅ compound showed by far the highest room-temperature coercivity.     

Synthesis of α-Fe2O3 nanobelts and nanoflakes by thermal oxidation and study to their magnetic properties

α-Fe₂O₃ nanobelts and nanoflakes have been successfully synthesized by oxidation of iron-coated ITO glass in air. The X-ray diffraction, Raman spectrum and scanning electron microscopy are carried out to characterize the nanobelts and nanoflakes. The formation mechanism has been presented. Significantly, the magnetic investigations show that the magnetic properties are strongly shape-dependent. The magnetization measurements of belt-like and flake-like α-Fe₂O₃ in perpendicular exhibit ferromagnetic feature with the coercivity (H_c) and saturation magnetization (M_s) of 334.5 Oe and 1.35 emu/g, 239.5 Oe and 0.12 emu/g, respectively. For the parallel, belt-like and flake-like α-Fe₂O₃ also exhibit ferromagnetic feature with the H_c and M_s of 205.5 Oe and 1.44 emu/g, 159.6 Oe and 0.15 emu/g, respectively.     

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.     

Ni–Zn–Sm nanopowder ferrites: Morphological aspects and magnetic properties

Ni–Zn ferrites have been widely used in components for high-frequency range applications due to their high electrical resistivity, mechanical strength and chemical stability. Ni–Zn ferrite nanopowders doped with samarium with a nominal composition of Ni_0.5Zn_0.5Fe_2−xSm_xO₄ (x=0.0, 0.05, and 0.1 mol) were obtained by combustion synthesis using nitrates and urea as fuel. The morphological aspects of Ni–Zn–Sm ferrite nanopowders were investigated by X-ray diffraction, nitrogen adsorption by BET, sedimentation, scanning electron microscopy and magnetic properties. The results indicated that the Ni–Zn–Sm ferrite nanopowders were composed of soft agglomerates of nanoparticles with a high surface area (55.8–64.8 m²/g), smaller particles (18–20 nm) and nanocrystallite size particles. The addition of samarium resulted in a reduction of all the magnetic parameters evaluated, namely saturation magnetization (24–40 emu/g), remanent magnetization (2.2–3.5 emu/g) and coercive force (99.3–83.3 Oe).     

Preparation and properties of cobalt oxides coated carbon fibers as microwave-absorbing materials

Cobalt oxides/carbon fibers (CoO_x/CFs) composites were synthesized by thermal oxidation of cobalt coated carbon fibers (Co/CFs). The scanning electron microscopy images and X-ray diffraction pattern indicate that the layers are about 0.7 μm and composed of Co₃O₄ and CoO (CoO_x), the preferred condition for preparation of CoO_x/CFs composites is to anneal Co/CFs precursors at 350 °C for 3 h in air. The coercivity, saturation magnetization and residual magnetization of the CoO_x/CFs composites are 464.8 Oe, 10.62 emu/g and 2.21 emu/g, respectively. The reflectivity of cobalt oxides coated carbon fibers (1.11-5.12 mm in thickness) is less than −10 dB over the working frequency range of 4.04-18.00 GHz and less than −20 dB over 11.54-14.77 GHz. The lowest reflectivity is −45.16 dB at 13.41 GHz when the thickness is 1.50 mm.     

High-temperature oxidation resistance and magnetic properties of Si-doped Sm2Co17-type magnets at 500 °C

The high-temperature oxidation resistance and magnetic properties of Si-doped Sm₂Co₁₇-type magnets at 500 °C were systematically investigated. The Sm(Co_0.76, Fe_0.1, Cu_0.1, Zr_0.04)₇Si_x (x=0–0.6) magnets were prepared by the conventional powder metallurgical technique. It is found that the addition of silicon in the Sm₂Co₁₇-type magnet can remarkably improve its oxidation resistance. Moreover, a small amount of silicon addition can also increase its high-temperature intrinsic coercivity. A maximum intrinsic coercivity of 6.7 kOe at 500 °C was obtained for the Sm₂Co₁₇-type magnet with Si content x=0.4, whose high-temperature maximum energy product loss was about 2.5 times smaller than pure Sm₂Co₁₇-type magnet after oxidation at 500 °C for 100 h, indicating the enhanced oxidation resistance. Its corresponding Curie temperature and saturation magnetization are about 723.9 °C and 7.4 kG, respectively.     

Effect of sputtering process on magnetic properties and crystal structure of Sm2Fe17Nx thin films

Hard magnetic Sm₂Fe₁₇N_x thin films were prepared by dc magnetron sputtering and subsequent nitrogenation process. The results show that the sputtering parameters determine the film composition, which determines the crystal structure and magnetic properties. When the gas pressure varies from 1.2 to 2.1 Pa and power varies from 40 to 60 W, higher Sm content (>11.3 at%) is obtained, giving rise to improved coercivity H_C and remanence ratio M_R/M_S. The optimal H_C of 2127.8 Oe and M_R/M_S of 0.53 are obtained when the gas pressure and power reach 1.2 Pa and 50 W, respectively. In addition, it is found that the pure single Sm₂Fe₁₇ phase can be observed when the ratio of Fe/Sm exceeds 7.1 by controlling the sputtering parameters to adjust the composition.     

Magnetic and structural properties of the electrochemically deposited arrays of Co and CoFe nanowires

Magnetic and structural properties of the arrays of 18 nm diameter nanowires of Co and Co₉₀Fe₁₀ electrodeposited in the pores of anodic alumina are investigated. Arrays of Co and Co₉₀Fe₁₀ nanowires show perpendicular magnetic anisotropy and textured crystallographic behaviour. Coercivity H_c (⊥) and remanence M_r/M_s (⊥) values of 2275 Oe (Co₉₀Fe₁₀); 1188 Oe (Co) and 96% (Co₉₀Fe₁₀), 81% (Co) are observed. The continuous films of Co and Co₉₀Fe₁₀ on Cu substrates show in plane magnetic anisotropy and coercivity values between 109 and 288 Oe.     

Solid-phase synthesis of Co7Sm2(110) epitaxial nanofilms: Structural and magnetic properties

The solid-phase synthesis of the Co₇Sm₂ and Co₁₇Sm₂ magnetically hard phases in Co/Sm/Co(110) epitaxial film systems has been experimentally investigated. The Co₇Sm₂ phase is first formed at the Sm/Co interface at a relatively low (～300°C) temperature. As the annealing temperature increases to ～450°C, the Co₁₇Sm₂(110) phase grows epitaxially on the Co₇Sm₂(110) phase. The saturation magnetization and biaxial anisotropy constant in the samples vary with the formation of the Co₇Sm₂ and Co₁₇Sm₂ phases. Investigations of the solid-phase synthesis in the nanofilms reveal the existence of a new structure phase transition at 300°C in the Co-Sm system with a high cobalt content.     

Structure and magnetic properties of nanocrystalline cobalt ferrite powders synthesized using organic acid precursor method

Nanocrystalline octahedra of cobalt ferrite CoFe₂O₄ powders were synthesized using the organic acid precursor route. The effect of the calcination temperature, Fe³⁺/Co²⁺ molar ratio, calcination time and type of organic acid (oxalic, benzoic and tartaric acids) on the formation, crystallite size, microstructure and magnetic properties was studied systematically. The Fe³⁺/Co²⁺ molar ratio was varied from 2 to 1.739 while the annealing temperature was controlled from 400 to 1000 °C for various periods from 0.5 to 2 h. The resulting powders were investigated using X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). XRD results indicate that a well crystallized, single spinel cobalt ferrite phase was formed for the precursors annealed at 600-800 °C for 2 h, using oxalic and tartaric acids as precursors for Fe³⁺/Co²⁺ molar ratio 1.818. The crystallite size of as-formed powders was in the range of 38.0-92.6 nm at different operating conditions. The calcination temperature and Fe³⁺/Co²⁺ molar ratio have a significant effect on the microstructure of the produced cobalt ferrite. The microstructure of the produced powders was found to be octahedra-shaped. The crystalline, pure cobalt ferrite powders with magnetic properties having a maximum saturation magnetization (76.1 emu/g) was achieved for the single phase at Fe³⁺/Co²⁺ molar ratio 1.818 and annealing temperature of 600 °C for 2 h using tartaric acid precursor.     

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.     

Effect of Co underlayer on soft magnetic properties and microstructure of FeCo thin films

High saturation magnetization soft magnetic FeCo (=Fe₆₅Co₃₅) films were prepared using a thin Co underlayer. The FeCo/Co films exhibited a well-defined in-plane uniaxial anisotropy with easy axis coercivity (H_ce) of 10 Oe and hard axis coercivity (H_ch) of 3 Oe, and a half reduction of H_c with H_ce=4.8 Oe and H_ch=1.0 Oe was obtained when the composition was adjusted to 25 at% Co. The effective permeability of the films remains flat around 250 to 800 MHz. The saturation magnetostriction was 5.2×10⁻⁵ and the intrinsic stress was 0.8 GPa in FeCo single layer, both were slightly reduced by Co underlayer. The Co underlayer changed the preferred orientation of the FeCo films from (2 0 0) to (1 1 0) but more significantly, reduced the average grain size from ∼74 to ∼8.2 nm. It also reduced the surface roughness from 2.351 to 0.751 nm. The initial stage and interface diffusion properties were examined by TEM and XPS.     

Hydrothermal-induced oriented growth of Fe–Co alloy and Sm-substituted magnetite nanowire composites

Fe–Co alloy and Sm³⁺-substituted magnetite nanowire composites (Co_xFe_1−x/Co_yFe_1−ySm_zFe_2−zO₄) have been synthesized via a hydrothermal method without using surfactants or templates. The effects of substitution on structure and morphology were investigated by powder X-ray diffraction, X-ray photoelectron spectroscopy, Mössbauer spectroscopy, and transmission electron microscopy (TEM). The TEM image shows that the average diameter of the magnetite nanowires is about 40 nm and the length is several micrometers. The z=0.1 composite shows relatively high saturation magnetization (92.3 emu/g) detected by a vibrating sample magnetometer. The possible growth mechanism of the nanowires is discussed on the basis of the crystal structure of the materials. From the perspective of thermodynamics, we explain the postulated mechanism of the hydrothermal reaction.     

Magnetic characterization of dual phase FeZrB soft magnetic alloy

The magnetic properties and the annealing process of Fe₇₈Zr₇B₁₅ amorphous ribbons are investigated by X-ray diffraction (XRD), differential scanning calorimetry, and vibrating sample magnetometer. The fully amorphous structure of the as-quenched ribbons is confirmed by the XRD pattern. The Curie temperature and the saturation magnetization M_s of the ribbons are 305 °C and 124.3 emu/g, respectively. Annealing at 550 °C can result in an increase in M_s with annealing time due to the increasing crystallized volume fraction of α-Fe phase. The optimized annealing process is established at 550 °C for 20-30 min with maximum M_s of 146.6 emu/g. The morphology of the ribbons annealed at 550 °C is observed by scanning electron microscopy, showing that nanocrystalline α-Fe grains are dispersed in an amorphous matrix.