Recent developments in hard magnetic materials

Summary Hard magnetic materials find ever-increasing uses in modern technology. Their importance is mainly in the domain of permanent magnets, but a variety of other applications is being offered to this class of materials, especially for what regards the areas of information storage, telecommunications and special electronic devices. These developments are connected to the emphasis that is more and more given to thin films having high magnetic anisotropy. The recernt advancement in the field of hard magnetic materials is among the best examples where technology depends to a great extent upon the continuous progress in the scientific knowledge. The research activity is characterized by the introduction of new classes of materials and continuous improvements in the preparation techniques both for what regards industrial processing and method for obtaining high quality materials in form of crystals, films or amorphous specimens. In this respect a special place must be reserved to rare earth transition metal compounds, a class of materals that attracted enormeous attention after the discovery by Hoffer and Strnat in 1966 of the large uniaxial magnetocrystalline anisotropy of the compound YCo₅. Beside the so called 1∶5 phase, other compositions of technical importance are the 2∶17 and the recently discovered Nd₂Fe₁₄B, which is a real new ternary phase having tetragonal crystal structure. Great efforts have been done to gain a better understanding of the magnetic anisotropy and its relationship to the coercivity is of leading importance for a further development in this important area of magnetism.     

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).     

Study of high-coercivity sintered NdFeB magnets

Magnetic powders for sintered NdFeB magnets have been prepared by using an advanced processing method including strip casting, hydrogen decrepitation, jet milling and rubber isotropic press. The effects of Dy, Ga and Co addition on the microstructure and magnetic properties of sintered magnets have been investigated. By adopting a suitable component ratio and adjusting proper technological parameters, we have prepared high-coercivity sintered NdFeB magnets with hard magnetic properties of _jH_c=25.6 kOe, B_r=13.2 kG and (BH)_max=39.9 MGOe. The temperature coefficient of coercivity of the magnets (between 20 and 150 °C) is –0.53%/°C. The magnetic properties at high temperature satisfy the needs of permanent magnet motors.     

Fe65B22Nd9Mo4 bulk nanocomposite permanent magnets produced by crystallizing amorphous precursors

The Fe₆₅B₂₂Nd₉Mo₄ nanocomposite permanent magnets in the form of a rectangular cross sectioned rod have been prepared by annealing the amorphous precursors. The thermal behavior, structure and magnetic properties of the magnets have been investigated by differential scanning calorimetry, X-ray diffractometry, electron microscopy and magnetometry techniques. The as-cast Fe₆₅B₂₂Nd₉Mo₄ alloy showed soft magnetic properties, which changed into magnetically hard after annealing. Results provoke that the magnetic properties of the alloy are sensitive to thermal processing conditions. The optimum hard magnetic properties with a remanence (B_r) of 0.56 T, coercivity (_iH_c) of 920.7 kA/m and maximum energy product (BH)_max of 50.15 kJ/m³ were achieved after annealing the alloy at 983 K for 10 min. The good magnetic properties of Fe₆₅B₂₂Nd₉Mo₄ magnets are ascribed to the exchange coupling between the nano-scaled soft α-Fe, Fe₃B and hard Nd₂Fe₁₄B magnetic grains.     

Manipulation of the magnetic exchange interaction in SmCo films with high thermal stability by controlling phase transformation

High thermal stability and tunable magnetic exchange interaction (MEI) in SmCo materials have been the critical problem in applications to magnetic recording media and nanocomposite permanent magnets. We constructed SmCo films with a high thermal stability and tunable MEI by controlling the phase transformation through properly increasing the Sm concentration (20.5–37.7 at.%) and controlling the annealing process. Microstructure studies show that the SmCo₅ phases ensure that the film has a high thermal stability. Moreover, we manipulated the MEI in the film with non-magnetic precipitated SmCo₂ particles in the vicinity of SmCo₅ particles. These results provide a novel way to tune the MEI in SmCo materials while maintaining a high thermal stability.     

Investigation on magnetic properties of orientated nanocomposite Pr2Fe14B/α-Fe permanent magnets by micromagnetic finite-element method

Demagnetization curves for nanocomposite Pr₂Fe₁₄B/α-Fe permanent magnets with different hard grain alignment are calculated by a micromagnetic finite-element method. The results show that both remanence and coercivity increase with improving hard grains alignment. The demagnetization curves show a single-phase demagnetization behavior for the samples with grain size d of 10 nm and two-phase behavior for the samples with d of 20 and 30 nm. H_ex (reflecting the magnetic hardening of α-Fe) and H_irr (expressing the irreversible reversal of hard phase) are both enhanced with improving the hard grain alignment. The magnetic reversal in orientated nanocomposite permanent magnets is mainly controlled by inhomogeneous pinning of the nucleated type.     

Evaluation of magnetic force distribution on a pair of superconducting bulk magnets

We study the construction of superconducting permanent magnets by RE123 bulk materials and the investigation of these industrial applications such as a magnetic separation. A bulk magnet can generate strong magnetic fields exceeding 2 T, which is the limit of ordinary iron-cored electromagnets, in a compact device with a low running cost. A magnetic field distribution of the bulk magnet is a cone shape, and it contributes to an increase of magnetic force which is proportional to the product of a magnetic field and its gradient. It is important to evaluate magnetic force when the application of the bulk magnet is discussed. In this paper, two Gd123 bulk materials of 65 mm in diameter were magnetized using a pair of superconducting bulk magnet system and three-axis components of magnetic flux density (B_x,⋅B_y, and B_z) in an open space between the magnetic poles were scanned with pitch of 2 mm in each direction. From these measured data, the axial and radial components of magnetic force factor, B_z⋅dB_z/dz and B_r⋅dB_r/dr, were calculated. At 10 mm gap, the B_z⋅dB_z/dz value reached 180.6 T²/m for a field of 2.33 T, which is comparable to B_z = 6.76 T for a common 10 T–100 mm∅ superconducting magnet.     

Nanophase hard magnets

The dramatic developments that occurred in nanophase hard magnetic materials over the last two decades are reviewed. Much of the research was done after the discovery of Nd₂Fe₁₄B-based magnets in an attempt to develop more economical Fe-based magnets with better properties. This led to the discovery of 1 : 12-based magnets, 2 : 17 nitrides and carbides, and more recently, to nanocomposite magnets consisting of a fine mixture of exchange coupled soft and hard phases. Currently, much emphasis is devoted to nanocomposite films consisting of nanoparticles of a high anisotropy material embedded in a non-magnetic matrix because they have a great potential for applications in high density recording media.     

Permanent magnet applications

Rare-earth permanent magnets are ideally suited to generate magnetic fields comparable to their spontaneous polarization J_S. Near-square hysteresis loops and large values of the coercivity and anisotropy fields greatly simplify magnet design, as each magnet block is effectively transparent to the magnetic fields produced elsewhere in the magnet assembly. The fields generated by compact and efficient magnet structures requiring no continuous expenditure of energy can be static or variable, uniform or nonuniform. Permanent magnets are fully competitive with electromagnets for fields up to 2 T, and fields as high as to 5 T can be produced in a small volume. When a field with a rapid spatial variation is required, permanent magnets may offer the only practicable solution. Both permanent magnet structures and the uses to which they are put are reviewed, classifying the magnet applications in terms of the nature of the field, the effect on the magnet and the physical effect exploited.     

Resin-bonded permanent magnetic films with out-of-plane magnetization for MEMS applications

Resin-bonded permanent magnets with out-of-plain direction of magnetization and improved magnetic properties for magnetic MEMS actuator have been created. The material investigated consists of magnetically anisotropic strontium ferrite particles embedded into epoxy resin matrix upto a volume loading of 80%. Intrinsic coercivity H_ci of 6000 Oe (480 kA/m), residual magnetic flux density B_r up to 4000 G (0.4 T) and maximum energy product (BH)_max of 3.0 MG Oe (23.6 kJ/m³) have been attained due to magnetic-field-induced alignment of the ferrite particles during curing process.     

Effect of γ-ray irradiation on the magnetic properties of NdFeB and Fe–Cr–Co permanent magnets

The effect of γ-ray irradiation on the magnetic properties of NdFeB and Fe–Cr–Co permanent magnets has been investigated. The magnetic flux loss of two kinds of magnets before and after irradiation was measured. Results show that the effect of γ-ray irradiation on the magnetic properties of sintered NdFeB is not so obvious as that on Fe–Cr–Co magnet. Irradiation-induced damage from γ-ray for the Fe–Cr–Co magnets was characterized for the first time. The decline of permanent magnetic properties of Fe–Cr–Co magnet induced by γ-ray irradiation is reversible except for the maximum energy product (BH)_max. The difference of coercivity mechanism between these two kinds of permanent magnets is responsible for the different dependence of magnetic properties loss induced by γ-ray irradiation.     

Analysis of the magnetic field, force, and torque for two-dimensional Halbach cylinders

The Halbach cylinder is a construction of permanent magnets used in applications such as nuclear magnetic resonance apparatus, accelerator magnets and magnetic cooling devices. In this paper the analytical expression for the magnetic vector potential, magnetic flux density and magnetic field for a two dimensional Halbach cylinder are derived. The remanent flux density of a Halbach magnet is characterized by the integer p. For a number of applications the force and torque between two concentric Halbach cylinders are important. These quantities are calculated and the force is shown to be zero except for the case where p for the inner magnet is one minus p for the outer magnet. Also the force is shown never to be balancing. The torque is shown to be zero unless the inner magnet p is equal to minus the outer magnet p. Thus there can never be a force and a torque in the same system.     

Evolution of phase,texture, microstructure and magnetic properties of Fe–Cr–Co–Mo–Ti permanent magnets

Magnetic phase evolution, crystallographic texture, microstructure and magnetic properties of Fe–28Cr–15Co–3.5Mo–1.8Ti alloy have been investigated by X-ray diffractometry, scanning transmission electron microscopy and magnetometry techniques as a function of processing conditions. Heat treatment conditions for obtaining optimum textural, microstructural and magnetic properties have been established by the experimentations. The Goss {110}〈001〉 and cube type {001}〈010〉 textures have been developed in an optimal treated Fe–28Cr–15Co–3.5Mo–1.8Ti magnets. The coercive force in Fe–28Cr–15Co–3.5Mo–1.8Ti magnets depends critically on the shape anisotropy of rod-like Fe Co Ti-rich α₁ particles and remanence on the alignment and elongation of α₁ particles parallel to applied magnetic field 〈100〉 directions. The optimum magnetic properties obtained in Fe–28Cr–15Co–3.5Mo–1.8Ti alloy are intrinsic coercive force, _iH_c, of 78.8 kA/m (990 Oe), remanence, B_r of 1.12 T (11.2 kG) and energy product, (BH)_max of 52.5 kJ/m³ (6.5 MGOe). The development of Fe–28Cr–15Co–3.5Mo–1.8Ti magnets as well as characterization of texture, microstructural and magnetic properties in the current study would be helpful in designing the new Fe–Cr–Co–Mo based magnets suitable for scientific and technological applications.     

Mixing characterization of mechanically milled Fe75Si15M10 powders using Mössbauer spectroscopy

Iron nitrides are attractive as they show excellent magnetic properties which can be utilized as recording and permanent magnetic materials for potential applications. Due to the high saturation magnetization and chemical stability, γ ^′-Fe₄N compound is widely investigated as a promising high density magnetic recording material. γ ^′-Fe₄N particles were synthesized by conventional gaseous nitriding in a heated atmosphere containing ammonia as a source of nitrogen. X-ray diffraction, ⁵⁷Fe Mössbauer spectroscopy, vibrating sample magnetometer, scanning electron microscopy and transmission electron microscopy are used for the characterization of the as prepared sample.     

Glass formation,magnetic properties and magnetocaloric effect of ternary Ho–Al–Co bulk metallic glass

A ternary Ho–Al–Co system with high glass-forming ability (GFA) was developed and fully glassy rods with diameters up to 1 cm can be produced for the best glass former of Ho₅₅Al_27.5Co_17.5 alloy. The thermal stability and low-temperature magnetic properties of the Ho₅₅Al_27.5Co_17.5 bulk metallic glass (BMG) were studied. The magnetic transition temperature of this alloy is ∼14 K as determined by the thermomagnetic measurement. Two indicators, i.e. isothermal magnetic entropy change (ΔS_M) and the relative cooling power (RCP), were adopted to evaluate the magnetocaloric effect (MCE) of the alloy under a low magnetic field up to 2 T, which can be generated by permanent magnets. The values of |ΔS_M| and RCP are 7.98 J kg⁻¹ K⁻¹ and 191.5 J kg⁻¹, respectively. The Ho₅₅Al_27.5Co_17.5 BMG with good MCE and high GFA provides an attractive candidate for magnetic refrigeration applications, like hydrogen liquefaction and storage.     

The effect of compound addition Dy2O3 and Sn on the structure and properties of NdFeNbB magnets

NdFeNbB with the additions of Dy₂O₃ and Sn permanent magnets have been attained by means of powder-blending technique, and their magnetic properties, temperature performance and microstructure were studied in this paper. The addition of just 2.0 wt% Dy₂O₃ or 0.3 wt% Sn proved to be very effective in improving the permanent magnetic properties of NdFeNbB magnets. Dy₂O₃ additions result in the increase in the H_ci and temperature dependence due to the increase of T_c, formation of (NdDy)-rich phase and grain refinement of Φ phase. This improvement of the coercivity stability of the magnets from the addition of Sn is attributed to the smoothing effect of the Sn addition at the grain boundaries. The magnetic properties, the temperature dependence and Curie temperature of NdFeNbB with Dy₂O₃ and Sn combined addition were found to be considerably improved. From the X-ray diffraction, SEM-EDAX studies and the thermo-magnetic study, the improved properties due to the solution of Dy and Sn to the Φ phase, the reduced N_eff and the smaller Φ phase.     

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.     

Magnetic sublattices in Np2Co17 and Np2Ni17

Rare-earth-based compounds R₂T₁₇ (R=Rare earth; T=Transition metal) have been extensively studied and developed for applications as permanent magnets. The actinide-based analogues, however, are much less documented and we report here about the magnetic properties of Np₂Co₁₇ and Np₂Ni₁₇, as inferred from ²³⁷Np Mössbauer spectroscopy, the best resonance in actinides, and specific heat.     

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.