Effects of powder flowability on the alignment degree and magnetic properties for NdFeB sintermagnets

The magnetic powders for sintered NdFeB magnets have been prepared by using the strip casting (SC), hydrogen decrepitation (HD) and jet milling (JM) techniques. The effects of powder flowability and addition of a lubricant on the alignment degree and the hard magnetic properties of sintered magnets have been studied. The results show that the main factor affecting powder flowability is the aggregation of magnetic particles for powders in a loose state, but it is the friction between the powder particles for powders that are in a compact state. The addition of a lubricant with suitable dose can slightly prevent the congregating of powders, obviously decrease the friction between the powder particles, improve the powder flowability, and increase the alignment degree, remanence and energy product density of sintered magnets. Mixing a suitable dose of lubricant and adopting rubber isostatic pressing (RIP) with a pulse magnetic field, we have succeeded in producing the sintered NdFeB magnet with high hard magnetic properties of B_r=14.57 KG, _jH_c=14.43 KOe, (BH)_max=51.3 MGOe.     

Production and corrosion resistance of NdFeBZr magnets with an improved response to thermal variations during sintering

This study describes an attempt to produce NdFeB magnets that are insensitive to the sintering temperature. It was found that addition of Zr to NdFeB magnets significantly augmented the thermal stability of this magnetic material during sintering at high temperature even at industrial scale. The best sintered magnets were produced by jet-milling the powder (to achieve an average 3.4 μm particle size), and then aligned, pressed and sintered under argon at 1100 °C for 3 h followed by appropriate heat treatment. The magnetic properties of the resulting magnets were: (BH)_m=403.8 kJ m⁻³ (±4.7 kJ m⁻³), B_r=1430 mT (±9 mT) and _iH_c=907 kA m⁻¹ (±12 kA m⁻¹). Large grain growth, in excess of 100 μm in the Zr-free magnets, was observed during sintering at 1100 °C. This did not occur in the presence of Zr. These observations imply that the sensitivity of this class of magnets to high sintering temperatures is greatly reduced by Zr addition. Corrosion resistance of NdFeB was therefore significantly improved by the addition of small amounts of Zr.     

Production for high thermal stability NdFeB magnets

To improve sintered NdFeB magnets’ thermal stability and magnetic properties, combined addition of elements Cu and Gd was investigated. It was found that with Gd addition increase to 1.0%, the temperature coefficient α improved from −0.15 to −0.05%/°C (maximum working temperature 120 °C), but the remanence and the maximum energy product linearly decreased. With addition of Cu in Gd-containing magnets the intrinsic coercivity increased greatly, and the remanence increased also because of their density improvement, and optimum Cu content was achieved at 0.2%. Microstructure analysis showed that most of the Cu distributed at grain boundaries and led to clear and smooth morphologies. Magnets with high thermal stability α=−0.05%/°C and magnetic properties were obtained with addition of Gd=0.8% and Cu=0.2%.     

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 properties of Nd–Fe–B film magnets prepared by RF sputtering

Highly oriented films of ∼6 μm in thickness consisting of the Nd₂Fe₁₄B compound phase were obtained by a three-dimensional sputtering method at room temperature and the subsequent crystallization by annealing. The c-axis orientation and coercivity of film samples were sensitive to the sputtering parameters and annealing conditions. The optimum temperature and time for annealing were 650 °C and 30 min to show the highest coercivity without any deterioration for the orientation of Nd₂Fe₁₄B grains, and furthermore the degree of c-axis orientation was increased by decreasing the Ar gas pressure or input power for sputtering. The resultant film magnets with good magnetic properties of B_r=∼1.06 T, H_C=∼371 kA/m, and (BH)_max=∼160 kJ/m³ were obtained under the optimized parameters for sputtering.     

Magnetic properties in Fe-doped NiO synthesized by co-precipitation

The magnetic properties of 1.5 at% Fe-doped NiO bulk samples were investigated. The samples were prepared by sintering the corresponding precursor in air at temperatures between 400 and 800 °C for 6 h. The synthesis was by a chemical co-precipitation and post-thermal decomposition method. In order to allow a comparison, a NiO/0.76 at% NiFe₂O₄ mixture was also prepared. The X-ray diffraction pattern shows that the samples that were sintered at 400 and 600 °C remain single phase. As the sintering temperature increased to 800 °C, however, the sample becomes a mixture of NiO and NiFe₂O₄ ferrite phases. The samples were investigated by measuring their magnetization as a function of magnetic field. The samples sintered between 400 and 800 °C and the one mixed directly with NiFe₂O₄ nanoparticles show a coercivity value of H_c≈200, 325, 350 and 110 Oe, respectively. The magnetic properties of the samples depend strongly on the sintering temperature. Simultaneously, the field-cooling hysteresis loop shift also observed after cooling the sample sintered at 600 °C to low temperature suggests the possibility of the existence of a ferromagnetic/antiferromagnetic exchange coupling.     

A preparation method and effects of Al–Cr coating on NdFeB sintered magnets

A 50 μm Al–Cr coating on NdFeB sintered magnets was prepared through dipping in solution, shaking dry and heating at 300 °C. The morphology and composition of the Al–Cr coating were investigated with scanning electron microscope, energy dispersive spectrometer and X-ray diffraction. The corrosion resistance of NdFeB sintered magnets with and without the Al–Cr coating was analyzed by normal salt spray, polarization curves and electrochemical impedance spectroscopy. The magnetic properties were measured with a hysteresis loop tracer. The results show that the Al–Cr coating forms an overlapping structure and Al flakes lie nearly parallel to the substrate, which improves the anticorrosion and increases normal salt spray test from 10 to 100 h. The corrosion potential of NdFeB sintered magnets with and without the Al–Cr coating moves positively from −0.67 to −0.48 V, which is in accordance with Nyquist and Bode plots. The Al–Cr coating has little influence on the magnetic properties of the NdFeB sintered magnets.     

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.     

The effects of annealing at 1000 °C for 24 h on the extrinsic properties of Pr-Fe-B and Nd-Fe-B-type sintered magnets

Recent studies have shown the effects of a post sintering heat treatment at 1000 °C for 24 h on the microstructure and magnetic properties of Pr-Fe-B/Nd-Fe-B magnets based on Nd₁₆Fe₇₆B₈ and Pr₁₆Fe₇₆B₈. In an attempt to understand the influence of environmental factors, an investigation into the effects of annealing under different degrees of vacuum for both types of sintered magnets has been carried out. The effect of annealing the Pr-Fe-B magnets at 1000 °C for 24 h resulted in a general increase in the magnetic properties, especially the intrinsic coercivity, although the degree of improvement appeared to be dependent on the initial annealing conditions (ambient pressure). Oxygen analysis of sintered and annealed magnets indicates a change in the nature of the grain boundary phases after the annealing treatment. The effect of annealing the Nd-Fe-B magnets at 1000 °C for 24 h resulted in a general decrease in the magnetic properties, especially the intrinsic coercivity.     

Effect of zinc concentration on the structural,electrical and magnetic properties of mixed Mn–Zn and Ni–Zn ferrites synthesized by the citrate precursor technique

Mixed manganese-zinc and nickel-zinc ferrites of composition Mn_0.2Ni_0.8−xZn_xFe₂O₄ where x=0.4$x=0.4$, 0.5 and 0.6 have been synthesized by the citrate precursor technique. Decomposition of the precursor at temperatures as low as 500 °C gives the ferrite powder. The ferrites have been investigated for their electrical and magnetic properties such as saturation magnetization, initial permeability, Curie temperature, AC-resistivity and dielectric constant as a function of sintering temperature and zinc content. Structural properties such as lattice parameter, grain size and density are also studied. The mixed compositions exhibited higher saturation magnetizations at sintering temperatures as low as 1200 °C. While the Curie temperature decreased with zinc content, the permeability was found to increase. The AC-resistivity ranged from 10⁵–10⁷ Ω cm and decreased with zinc content and sintering temperature. The dielectric constants were lower than those normally reported for the Mn–Zn ferrites. Samples sintered at 1400 °C densified to about 94% of the theoretical density and the grain size was of the order of about 1.5 μm for the samples sintered at 1200 °C and increased subsequently with sintering temperature.     

Synthesis and magnetic study on Mg-substituted Li-Mn spinel oxides

LiMn_2−xMg_xO₄ (X<0.5) cubic spinel oxide was synthesized by the sol-gel technique using Li-nitrate, Mn-acetate and Mg-acetate salts. The gel precursors were decomposed at 300 °C in air and then annealed at temperatures ranging from 500 to 850 °C in an oxygen flow. For a fixed annealing temperature of 700 °C, the lattice constant decreased with an increase in the substitution degree X and a discontinuity was found around X=0.3. With a further increase in X>0.3, the space group of the crystal structure was converted from Fd3m to P4₃32 by the cation ordering in the octahedral site. The low-temperature magnetization increased with X, and the Weiss constant moved in the positive direction and changed its sign from negative to positive around X=0.3. In the case of X=0.5, all the specimens showed P4₃32 structure and ferromagnetic character. The maximum Curie temperature (T_c=23 K) and the maximum magnetization (M_s=4.68 μ_B per the chemical formula unit) were attained simultaneously for the specimen obtained around 700 °C. The Mn valence state was sensitive not only to the substitution but also to the preparation conditions. Hence, it was possible to explain these variations by considering the magnetic interactions between transition metal ions.     

Effect of Mn-site vacancies on the magnetic entropy change and the Curie temperature of La0.67Ca0.33Mn1−xO3 perovskite

Single-phase polycrystalline samples of La_0.67Ca_0.33Mn_1−xO₃ (x=0.00, 0.02, 0.04, 0.06) have been prepared using the sol-gel method. The structure, magnetocaloric properties and the Curie temperature of the samples with different Mn vacancy concentrations have been investigated. The experimental results show that vacancy doping at the Mn-sites has a significant influence on the magnetic properties of La_0.67Ca_0.33Mn_1−xO₃. The Curie temperature decreases monotonically with increasing the Mn-site vacancy concentration x. A remarkable enhancement of the magnetic entropy change has been obtained in the La_0.67Ca_0.33Mn_0.98O₃ sample. The entropy change reaches |ΔS_M|=3.10 J kg⁻¹ K⁻¹ at its Curie temperature (264 K) under an applied magnetic field H=10 kOe, which is almost the same value as that of pure Gd.     

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.     

Double-peak resistivity transport properties of La0.67Ca0.33MnO3 ceramics

Polycrystalline samples of La_0.67Ca_0.33MnO₃ were prepared by solid-state reactions by varying the pelletization force and the sintering temperature. Lowering the sintering temperature gave rise to smaller grains and increased the overall resistivity of the ceramic. Partial melting was observed in the ceramics sintered at higher temperatures (1400-1500 °C). Additionally, these ceramics showed two distinct resistivity peaks. The resistivity peak near the magnetic transition (T_C) was sharp, whereas the second peak was a broad one observed below T_C.     

The effect of B2O3 addition to the microstructure and magnetic properties of Ni0.4Zn0.6Fe2O4 ferrite

The effects of 0.01 and 0.1 mol B₂O₃ addition to the microstructure and magnetic properties of a Ni–Zn ferrite composition expressed by a molecular formula of Ni_0.4Zn_0.6Fe₂O₄ were investigated. The toroid-shaped samples prepared by pressing the milled raw materials used in the preparation of the composition were sintered in the range of 1000–1300 °C. The addition of 0.01 mol B₂O₃ increased the grain growth and densification giving rise to reduced intergranular and intragranular porosity due to liquid-phase sintering. The sintered toroid sample at 1300 °C gave the optimum magnetic properties of B_r=170 mT, H_c=0.025 kA/m and a high initial permeability value of μ_i=4000. The increment of the B₂O₃ content to 0.1 mol resulted in a pronounced grain growth and also gave rise to large porosity due to the evaporation of B₂O₃ at higher sintering temperatures. Hence, it resulted in an air-gap effect in the hysteresis curves of these samples.     

Structural,magnetic and electrical properties of Co1−xZnxFe2O4 synthesized by co-precipitation method

Nanoparticles of Co_1−xZn_xFe₂O₄ with stoichiometric proportion (x) varying from 0.0 to 0.6 were prepared by the chemical co-precipitation method. The samples were sintered at 600 °C for 2 h and were characterized by X-ray diffraction (XRD), low field AC magnetic susceptibility, DC electrical resistivity and dielectric constant measurements. From the analysis of XRD patterns, the nanocrystalline ferrite had been obtained at pH=12.5–13 and reaction time of 45 min. The particle size was calculated from the most intense peak (3 1 1) using the Scherrer formula. The size of precipitated particles lies within the range 12–16 nm, obtained at reaction temperature of 70 °C. The Curie temperature was obtained from AC magnetic susceptibility measurements in the range 77–850 K. It is observed that Curie temperature decreases with the increase of Zn concentration. DC electrical resistivity measurements were carried out by two-probe method from 370 to 580 K. Temperature-dependent DC electrical resistivity decreases with increase in temperature ensuring the semiconductor nature of the samples. DC electrical resistivity results are discussed in terms of polaron hopping model. Activation energy calculated from the DC electrical resistivity versus temperature for all the samples ranges from 0.658 to 0.849 eV. The drift mobility increases by increasing temperature due to decrease in DC electrical resisitivity. The dielectric constants are studied as a function of frequency in the range 100 Hz–1 MHz at room temperature. The dielectric constant decreases with increasing frequency for all the samples and follow the Maxwell–Wagner's interfacial polarization.     

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.     

Magnetic properties of the Ce2Fe17−xMnx helical magnets up to high magnetic fields

Magnetic properties of the Ce₂Fe_17−xMn_x, x=0–2, alloys in magnetic fields up to 40 T are reported. The compounds with x=0.5–1 are helical antiferromagnets and those with 1<x?2 are helical ferromagnets or helical antiferromagnets at low and high T, respectively. Mn ions in the system carry average magnetic moment of 3.0±0.2 μ_B that couple antiparallelly to the Fe moments. Easy-plane magnetic anisotropy in the Ce₂Fe_17−xMn_x compounds weakens upon substitution of Mn for Fe. The absolute value of the first anisotropy constant in the Ce₂Fe_17−xMn_x helical ferromagnets decreases slower with increasing temperature than that calculated from the third power of the spontaneous magnetization. Noticeable magnetic hysteresis in the Ce₂Fe_17−xMn_x, x=0.5–2, helical magnets over the whole range of magnetic fields reflects mainly irreversible deformation of the helical magnetic structure during the magnetization of the compounds. A contribution from short-range order (SRO) magnetic clusters to the magnetic hysteresis of the helical magnets has been also estimated.     

Effect of sintering temperature on the structural, dielectric and ferroelectric properties of tungsten substituted SBT ceramics

Structural, dielectric and ferroelectric properties of tungsten (W) substituted SrBi₂(Ta_1−xW_x)₂O₉ (SBTW) [x=0.0, 0.025, 0.05, 0.075, 0.1 and 0.2] have been studied as a function of sintering temperature (1100-1250 °C). X-ray diffraction patterns confirm the single-phase layered perovskite structure formation up to x=0.05 at all sintering temperatures. The present study reveals an optimum sintering temperature of 1200 °C for the best properties of SBTW samples. Maximum T_c of ∼390 °C is observed for x=0.20 sample sintered at 1200 °C. Peak-dielectric constant (ε_r) increases from ∼270 to ∼700 on increasing x from 0.0 to 0.20 at 1200 °C sintering temperature. DC conductivity of the SBTW samples is nearly two to three orders lower than that of the pristine sample. Remnant polarization (P_r) increases with the W content up to x≤0.075. A maximum 2P_r (∼25 μC/cm²) is obtained with x=0.075 sample sintered at 1200 °C. The observed behavior is explained in terms of improved microstructural features, contribution from the oxygen and cationic vacancies in SBTW. Such tungsten substituted samples sintered at 1200 °C exhibiting enhanced dielectric and ferroelectric properties should be useful for memory applications.