Constitution of melt-spun NdFeB-magnets studied by analytical field ion microscopy

An analytical field ion microscope was applied to melt-spun NdFeB magnets with various cobalt substitutions. The microstructure of melt-spun NdFeB magnets consists of three phases. Whereas the Nd₂Fe₁₄B- and the metastable Nd₇Fe₃-phase determine the magnetic properties of optimally quenched specimens the Nd_1.1Fe₄B₄-phase additionally influences the magnetic behaviour of overquenched and annealed material. With Co substitution the Nd-rich phase transforms via the metastable Nd₂₃(Fe_1−xCo_x)₇₅B₂ intermediate stage of optimally quenched specimens to the stable Nd(Fe_1−xCo_x)₂-phase in over-quenched and annealed ribbons. From our experimental data we conclude that a nucleation model of coercivity is consistent with the magnetic measurements.     

Solidification structures in rapidly quenched Cu-Ti-Zr alloys

The melt-spinning and pulsed laser-quenching techniques were used to generate fast cooling rates necessary to form metallic glass in ternary Cu-Ti-Zr alloys. Even though the cooling rates generated during melt-spinning were much lower than those generated during pulse laser-quenching, the amount of glass obtained in the melt spun alloys was much larger than in the laser-quenched alloys. The microstructure of the laser-quenched alloys consisted of metallic glass and a fine microcrystalline fcc phase, whereas the melt-spun ribbons of the same compositions were completely amorphous. Glass transition temperature trends in the ternary system were determined from alloys of composition traversing linearly from the binary Cu-Ti side to the Cu-Zr side. These trends showed a nearly linear change of T_g with composition.     

Crystallographic alignment and magnetic anisotropy in melt-spun Nd-Fe-B/α-Fe composite ribbons with different neodymium contents

Crystallographic alignment and magnetic anisotropy were studied for NdxFe94-xB6 (x=8,9,10,11) ribbons prepared via melt-spinning. Effect of Nd content and wheel speed on the crystal structure and magnetic properties of the ribbons was investigated. Both the free and wheel side of the ribbons could obtain strong c-axis crystal texture of Nd2Fe14B phase perpendicular to the ribbons surface at low wheel speed,but the texture weakened gradually with the increase of the wheel speed. Increase of Nd content led to better formation of crystal texture in the ribbons,indicating that the α-Fe phase might undermine the formation of crystal texture. Magnetic measurement results showed that the magnetic anisotropy of the ribbons exhibited corresponding behavior with the invariance of the c-axis crystal texture of Nd2Fe14B phase in the ribbons,and the coercivity of the ribbons rose with the increase of both Nd content and wheel speed during melt-spun process.     

Magnetic properties of melt-spun ribbons(Sm_(1-x)Zr_x)(Fe_(0.92)Ti_(0.08))_(10) with ThMn_(12) structure and their hydrides

The structure and magnetic hysteresis properties of the cast Sm_(1-x)Zr_x(Fe_(0.92)Ti_(0.08))_(10)(x = 0-0.3)alloys and melt-spun ribbons prepared from them were studied.In the cast alloy with x0.2, a considerable amount of the eutectic phase is found in the SEM micrographs.Analysis of the temperature dependences of the magnetic susceptibility and XRD patterns allows amorphous state in the as-spun ribbons with x0.2 to be determined.The specific magnetization measured in a field of 17 kOe and remanence decrease with increasing annealing temperature from 800 to 900 ℃ and weakly depend on Zr concentration.The maximal value of coercivity Hc = 4.7 kOe is obtained on the ribbons with x = 0.2 after annealing at 850℃ for 10 min.After additional hydrogenation of the ribbons,both the coercivity and remanence increase by 54% and 7%,respectively.     

Preferred Orientation in Nanocomposite Permanent Magnet Materials

Melt-spun （Nd11.4Fe82.9B5.7）0.99M1 ribbons （M = Zr, Nb, Ga, Zr＋ Ga, Nb ＋ Ga）were prepared by melt-spinning technique. Ga addition is found to be effective for the orientation of c-axis of Nd2Fe14B grains perpendicular to the ribbon plane. Better magnetic properties can be achieved by adding both the two kinds of elements Zr ＋ Ga, Nb ＋ Ga, and it is found that the preferred orientation is further improved. The alignment degree changes with ribbon thickness and is highest when ribbon thickness is 120 μm. Heat treatment can improve the texture degree, but lead to coarser grains. Cryogenic treatment is first applied for the treatment of nanocomposite Nd2Fe14B/α-Fe melt-spun ribbons. The effects on magnetic properties and texture degree of nanocomposite magnets after cryogenic treatment were studied. The result shows that cryogenic treatment is beneficial to the enhancement of texture degree of melt-spun ribbon and the grain size has no obvious change.     

Effect of niobium substitution on microstructures and thermal stability of TbCu7-type Sm–Fe–N magnets

This paper reports crystal structures, magnetic properties and thermal stability of TbCu7-type Sm_(8.5)Fe_((85.8-x)Co_(4.5)Zr_(1.2)Nb_x(x = 0-1.8) melt-spun compounds and their nitrides, investigated by means of X-ray diffraction, vibrating sample magnetometer, flux meter and transmission electron microscope. It is found that the lattice parameter ratio c/a of TbCu_7-type crystal structure increases with Nb substitution, which indicates that the Nb can increase the stability of the metastable phase in the Sm-Fe ribbons. Nb substitution impedes the formation of magnetic soft phase a-Fe in which reversed domains initially form during the magnetization reversal process. Meanwhile, Nb substitution refines grains and leads to homogeneous micro structure with augmented grain boundaries. Thus the exchange coupling pining field is enhanced and irreversible domain wall propagation gets suppressed. As a result, the magnetic properties are improved and the irreversible flux loss of magnets is notably decreased. A maximum value 771.7 kA/m of the intrinsic coercivity H_(cj) is achieved in the 1.2 at% substituted samples.The irreversible flux loss for 2 h exposure at 120 ℃ declines from 8.26% for Nb-free magnets to 6.32% for magnets with 1.2 at% Nb substitution.     

Effect of cobalt substitution on structure and magnetic properties of Nd_(0.4)Zr_(0.6)Fe_(10-x)Co_xSi_2(x =0-3) alloys and their ribbons

This study reports the stabilization of the RFe_(12)-type based compounds where part of R and Fe are substituted with Zr and Co and Si, respectively, in order to examine whether these rare-earth-lean materials are suitable for applications as permanent magnets. Structural and magnetic characterization of the family of alloys with the general formula Nd_(0.4) Zr_(0.6) Fe_(10-x)Co_xS_i2(x = 0 -3) and their melt-spun ribbons were carried out using X-ray diffraction and M€ossbauer spectroscopy. The ThMn_(12)-type structure is obtained for all samples as the majority phase with a minority a-Fe(CoSi) phase(less than 5 wt%) as it was estimated by XRD for x = 1 and 2. The Curie temperature increases linearly with Co substitution from 561 K for x = 0 to 712 K for x = 3. The saturation magnetization decreases slightly from 130.5(x =1)to 129.1 A·m~2/kg(x=3), while the anisotropy field is following the same trend.     

Effect of Al82.8Cu17Fe0.2 alloy doping on structure and magnetic properties of SmCo5-based ribbons

This work tries to improve the magnetic properties by multi-element doping in the form of a ternary alloy.SmCo₅₊χwt%Al-Cu-Fe(x=0-7)ribbons melt-spun at 40 m/s were produced by adding Al_82.8Cu₁₇Fe_0.2alloy into SmCo₅ matrix,and their phases,microstructure,and magnetic properties were investigated.The results show that both x=0 and 3 ribbons form a cellular microstructure.Al-Cu-Fe addition reduces the content of the Sm₂(Co,M)₇ cell wall,narrows its width,and forms the local disordered micro-regions and solute-segregation nanoclusters in the Sm(Co,M)₅ grains.With x increasing to5,Al-Cu-Fe addition promotes the phase separation between and within grains of the SmCo₅-based alloy.The Al-Cu-Fe addition can simultaneously improve the coercivity and magnetization of the SmCo₅-based ribbons,in particular,the magnetization of the x=3 ribbons increases by 35%,while the coercivity of the x=5 ribbons increases by 3.9 times.Finally,the microstructure evolution models are built up,and the relationship between the microstructure and the magnetic properties is discussed.     

Unique metallic glass formability and ultra-high tensile strength in AlNiFeGd alloys

The metallic glass formability of aluminum-rich AlNiFeGd alloys has been systematically investigated. The critical cooling rate required to form an amorphous state in this system is generally low, and comparable to that of some of the best metallic glass formers, such as PdCuSi. Amorphous ribbons up to 0.25 mm thick can easily be produced by the single-roller melt-spinning technique. Tensile strengths as high as 1280 MPa and Young's modulus of 75 GPa have been obtained. Bulk amorphous alloys with good mechanical properties are optimized in Al₈₅Ni₆Fe₃Gd₆. DSC and DTA studies reveal that the glass formability is unique for Al-based alloys because the reduced glass temperature T_rg for AlNiFeGd can be as low as 0.44. This is much lower than conventional theory would suggest for easy glass forming systems. A mechanism for the unusual glass formability is suggested.     

Coercivity enhancement of nanocrystalline hot-deformed Nd-Fe-B magnets by low-melting eutectic MM-Cu(MM=La,Ce,Pr,Nd) alloys addition

MM_(85)Cu_(15)(MM = La,Ce,Pr,Nd) eutectic alloys were added into the hot-deformed Nd-Fe-B magnets to enhance the coercivity.It is found that three endothermic peaks occur on the differential scanning calorimetry curve of the MM-Cu melt-spun ribbons at 432.2,451.1 and 516.5℃.The peaks substantially correspond to three types of MM-Cu low-melting eutectic phase.The coercivity of magnets increases when the MM-Cu content is lower than 4 wt%,and then keeps almost no change with the content further increasing to 5 wt%.The coercivity of the hot-deformed magnets with 4 wt% and without MM-Cu addition is 948 and 683 kA/m,respectively.Nearly all the platelet-shaped grains are isolated by the thickened intergranular phase after MM-Cu addition.Moreover,the average grain size of the magnets with MM-Cu addition decreases compared with that of the magnet without MM-Cu addition.Scanning electron microscopy images show that the areal fraction of the RE-rich grain boundary phase increases from 8.6% to 15.1% after MM-Cu addition.The La,Ce together with Cu and Ga aggregate at the grain boundary regions separating neighboring grains and smoothing the grain boundaries.Therefore,both the thickened grain boundary and decreased mean grain size result in the enhancement of coercivity after MM-Cu eutectic alloy addition.     

Magnetic Alignment Study of Hybrid Magnet Consisting of R-Rich and R-Lean Nd-Fe-B Alloys

A hybrid magnet was prepared by the hot-pressing and die-upsetting of the mixture of the R-rich Nd_xFe_93.5–xGa_0.5B₆ (x= 13.5 and 11.8) alloy and the R-lean Nd_xFe_93–xNb₁B₆ (x = 6, 9) alloy melt-spun ribbons. The microstructure and magnetic properties of the hybrid magnet were investigated. In the hot-pressed or die-upset hybrid magnet the R-rich and R-lean alloy regions existed independently without alloying between them. The two alloy regions in the die-upset hybrid magnet were coupled effectively via a magnetostatic interaction. A texture was developed only in the R-rich Nd₂Fe₁₄B single phase alloy region in the die-upset hybrid magnet, and this led to an anisotropic nature in die-upset hybrid magnet. The die-upset hybrid magnets containing higher Nd-content (13.5 at%) host alloy shows consistently a better magnetic alignment with respect to the magnets with lower Nd-content (11.8 at%) host alloy.     

Influence of Heat Treatment on Microstructures and Properties of Nd8Fe78B6Co4 Alloy

Melt-spun Nd8Fe78B6Co4 magnetic powders and their bonded magnets were prepared with the optimization of compositions and preparation techniques. The microstructure change of alloy NdFeB and the relation between microstructure and heat-treatment were studied. The heat-treatment temperature is 200～700 ℃. The as-cast structure of the alloy is typically amorphous. Different melt-spun speed and different heat treatment could result in different magnetic properties of NdFeB magnets. Magnetic properties of NdFeB increase with the addition of element Co. The magnetic properties of magnet alloy get the best when the melt-spun speed reaches 23～26 m·s-1, heat treatment temperature is 690 ℃ and time is 30 min.     

Magnetoimpedance, magnetoinductance and AC magnetoresistance studies on amorphous and nanocrystalline ribbons

A systematic investigation of the influence of Al and V on the magnetoimpedance (MI), magnetoinductance (mi) and AC Magnetoresistance (ACMR) effect in melt-spun Fe_73.5Si_13.5B₈CuNb_(3?x)V_xAl (x=0,1,1.5,3) ribbons has been performed in the frequency range 500 kHz — 13 MHz and under dc magnetic field (H _ext ) up to 60 Oe. Nanocrystals of α-FeSi were observed, when annealed at 500°C in vaccum. MI, mi and ACMR were measured using impedance analyzer. Largest peak mi, MI and ACMR of 1615%, 61% and 69% were observed for the nanocrystalline x=1.0 ribbon, at 100 kHz, 10 MHz and 13 MHz respectively. Magnetic domain structure was studied in the ribbons through magnetic force microscopy.     

Evolution of crystallographic alignment in Tb-Fe-B melt-spun ribbons

Ternary Tb-Fe-B ribbons were prepared via melt-spun technique under different wheel speeds of 5-25 m/s. Effect of wheel speed on the crystal structure and microstructure of the ribbons was investigated. All the ribbons quenched under different wheel speeds crystallized in single Tb₂Fe₁₄B phase with tetragon structure. Different crystallographic alignment evolutions were observed in the free side surface and wheel side surface of the ribbons. On the free-side surface, an in-plane c-axis crystal texture of Tb₂Fe₁₄B phase was found in the ribbons quenched at 5 m/s. However, with the increase in the wheel speed, the direction of the c-axis texture turns to perpendicular to the ribbon surface. On the wheel-side surface, a strong c-axis texture perpendicular to the ribbon surface was observed in the ribbons quenched at 5 m/s, and then weakened gradually with the increase in the wheel speed. Further investigation showed that the competition of the two types of temperature gradients during the quench process was responsible for the crystallographic alignment evolution in the ribbons.     

Effect of wheel speed on phase formation and magnetic properties of (Nd0.4La0.6)-Fe-B melt-spun ribbons

The effect of wheel speed on phase formation and magnetic properties of (Nd_0.4La_0.6)₁₅Fe_77.5B_7.5 and (Nd_0.4La_0.6)_13.4Fe_79.9B_6.7 ribbons prepared by melt-spinning method was investigated experimentally. Based on X-ray diffraction results, all melt-spun ribbons consist of the main phase with the tetragonal 2:14:1 type structure and the minor α-Fe phase. Magnetic measurements show the maximum magnetic energy product ((BH)_max) and the remanence (M_r) increases firstly and then decreases with the increase of wheel speed, while the coercivity (H_ci) increases, resulting from the variation of the average volume fraction of the α-Fe phase and the average grain size in the melt-spun ribbons. Using Henkel plots, the interaction between the 2:14:1 phase and the α-Fe phase in the melt-spun ribbons was analyzed and the intergranular exchange coupling is manifested. Optimal magnetic properties of H_ci = 7.27 kOe, M_r = 90.94 emu/g and (BH)_max = 12.10 MGOe are achieved in the (Nd_0.4La_0.6)₁₅Fe_77.5B_7.5 ribbon with the wheel speed of 26 m/s. It indicates that magnetic properties of Nd-Fe-B melt-spun ribbons with highly abundant rare earth element La can be improved by optimizing alloy composition and preparation process.     

Effect of Terbium addition on the coercivity of the sintered NdFeB magnets

The effects of Tb addition on the microstructure and magnetic properties of the NdFeB magnets prepared by HD method were investigated by X-ray diffraction (XRD) and BH magnetometers. The results of the microstructure showed that both the Tb-doped and undoped permanent magnets were composed mostly of Tetragonal phase Nd₂Fe₁₄B (space group P42/mnm) and a trace amount of Nd-rich phase. Accordingly, addition of Tb led to a decrease of the pole density factor of (004), (006) and (008) crystal plane of the Nd₂Fe₁₄B phase calculated by Horta formula, but the coercivity of the magnets increased from 2038 kA/m up to 2302 kA/m as a consequence of Tb addition. The study of the H_c(T)/M_s(T) versus H^min_N/(M_s(T) behavior showed that the nucleation was the dominating mechanism for the magnetization reversal in both sintered magnets, and the microstructural parameters of α_k and N_eff were obtained also. The Kronmüller-plot showed an increase of the α_k responsible for an increase of the coercivity.     

The microstructure and magnetization reversal behavior of melt-spun (Nd1−xCex)-Fe-B ribbons

In this study,the alloy ingots with nominal compositions of(Nd_(1-x)Ce_x)_(31)Fe_(bal)Co_(0.2)Ga_(0.1)B(x=0, 0.1 wt%,0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%) were prepared and then melt-spun to form nanocrystalline ribbons at the wheel speed of 20 m/s. XRD results show that all melt-spun ribbons exhibit the tetragonal structure(Nd,Ce)_2 Fe_(14)B phase with the space group P42/mmm. The Curie temperature and lattice constant decrease with the increase of Ce content. The Curie temperature decreases gradually from 306 to 247 ℃with the increase of Ce content. Those results indicate that Ce element has been incorporated into Nd_2 Fe_(14)B main crystalline phase and formed(Ce,Nd)-Fe-B hard magnetic phase. It is also found that the remanence ratio(M_r/M_s) decreases from 0.693 to 0.663 and the coercivity(H_c) decreases from 18.7 to14.2 kOe with the increase of Ce content. However, a relatively high coercivity of 18.3 kOe for(Nd_(1-x)Ce_x)_(31)Fe_(bal)Co_(0.2)Ga_(0.1)B(x = 0.2) melt-spun ribbon is achieved. The coercivity is sensitive to microstructure. The AFM patterns show the sample(x = 0.2) has the most uniform and finest microstructure. The magnetization reversal behavior(δM plots) is discussed in detail. The positive δM value is observed in every sample, which confirms the existence of exchange coupling interaction. Evidently, theδM maximum value reaches 0.9 in the sample(x = 0.2). It is indicated that the intergranular exchange coupling effect is the strongest, which is consistent with coercivity enhancing.     

Magnetocaloric effect in ErNi_2 melt-spun ribbons

ErNi2 ribbons were produced by rapid solidification using the melt spinning technique.Their structural,magnetic and magnetocaloric properties in the as-solidified state were studied by X-ray diffraction,scanning electron microscopy,magnetization and specific heat measurements.Samples are single phase with the MgCu_2-type crystal structure,a Curie temperature T_C of 6.8 K and a saturation magnetization at2 K and 5 T of 124.0 A·m~2/kg.For a magnetic field change μ_0△H of 5 T(2 T) ribbons show a maximum magnetic entropy change |△S_M~(peak)| of 24.1(16.9) J/(kg·K),and an adiabatic temperature change △T_(ad)~(max) of8.1(4.4) K;this is similar to the previously reported literature for bulk alloys that were processed through conventional melting techniques followed by prolonged thermal annealing.In addition,the samples also show slightly wider △S_M(T) curves with respect to bulk alloys leading to a larger refrigerant capacity.     

Influence of Fe Content on Microstructure and Magnetic Properties of Melt-Spun SmCo-Based Alloy Ribbons

The microstructure and magnetic properties of melt-spun Sm(Co_0.88-xFe_xCu_0.10Zr_0.02)_7.5 (x = 0.1 and 0.2) alloy ribbons have been studied. The results showed that the as-spun ribbons were in a single phase, SmCo₇, with the Cu₇Tb structure. When aged in the temperature range from 720 to 900 °C, the SmCo₇ phase transformed into Sm₂Co₁₇, SmCo₅, and CoFe(Zr) phases with a minor Sm₂Co₃ phase. For the x = 0.1 alloy, a large coercivity, H_c = 8.7 kOe, was observed although the soft magnetic CoFe(Zr) phase was present in the alloy. The volume fraction of the CoFe(Zr) phase increased when the ageing temperature increased from 720 to 760 °C. At higher ageing temperature, the CoFe(Zr) phase was partially re-dissolved. With an increase in the Fe content in the alloy, the CoFe(Zr) phase increased significantly, causing the coercivity to decrease.