Improvement of coercivity and thermal stability of Nd-Fe-B sintered magnets by intergranular addition of Tb80Fe20 alloy

To improve the coercivity and temperature stability of Nd-Fe-B sintered magnets for high-temperature applications, the eutectic Tb₈₀Fe₂₀ (wt%) alloy powders were added into the Nd-Fe-B sintered magnets by intergranular method to enhance the coercivity (H_cj) and thermal stability. The microstructure, magnetic properties and thermal stability of the Nd-Fe-B magnets with different Tb₈₀Fe₂₀ contents were studied. The experimental results demonstrate that the coercivity (H_cj) of the sintered Nd-Fe-B magnet is significantly enhanced from 14.12 to 27.78 kOe, and the remanence (B_r) decreases not obviously by introducing 4 wt% Tb₈₀Fe₂₀ alloy. Meanwhile, the reversible temperature coefficients of coercivity (β) and remanence (α) of the Nd-Fe-B magnets are increased from ?0.5634%/℃ to ?0.4506%/℃ and ?0.1276%/℃ to ?0.1199%/℃ at 20–170 ℃, respectively. The Curie temperature (T_C) of the Nd-Fe-B magnet is slightly enhanced with the increase of Tb₈₀Fe₂₀ content. Moreover, the irreversible flux magnetic loss (h_irr) is obviously reduced as Tb₈₀Fe₂₀ addition increases. Further analysis of the microstructure reveals that a modified microstructure, i.e. clear and continuous RE-rich grain boundary layer, is acquired in the sintered magnets by introducing Tb₈₀Fe₂₀ alloy. The associated mechanisms on improved coercivity and thermal stability were comprehensively researched.     

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.     

Microstructure evolution and coercivity mechanism of hydrogenation-disproportionation-desorption-recombination (HDDR) treated Nd-Fe-B strip cast alloys

In this paper, we systematically investigated the microstructure evolution and coercivity mechanism of hydrogenation-disproportionation-desorption-recombination (HDDR) treated Nd-Fe-B strip cast alloys by transmission electron microscopy (TEM) and three-dimensional atom probe (3DAP) analyses. The rod-like NdH_2+x phases with diameters of 10–20 nm are embedded into α-Fe matrix, which hereditarily leads to textured grains in HDDR alloy. The migration of NdH_2+x from Nd-rich region to α-Fe matrix during hydrogen absorption process contributes to the uniform redistribution of Nd-rich phases after HDDR treatment. The HDDR alloy with single domain grain sizes of 200–300 nm exhibits relatively low coercivity of 1.01 T that arises from pinning magnetic domain motion. The weak c-axis orientation of HDDR alloy results in a lower reverse magnetic field (coercivity) to reduce remanence to 0. Moreover, the direct contact of Nd₂Fe₁₄B grains and the high concentration of ferromagnetic elements (Fe content ≈ 66.06 at%, Co content ≈ 0.91 at%) in Nd-rich grain boundary layer lead to strong magnetostatic coupling effect among Nd₂Fe₁₄B grains. The nano-sized α-Fe inside Nd₂Fe₁₄B matrix makes the magnetization reversal easily and decreases the coercivity of HDDR alloy.     

A comparison study of hydrogen storage performances of SmMg11Ni alloys prepared by melt spinning and ball milling

The melt spinning(MS) and ball milling(BM) technologies are thought to be efficient to prepare nanostructured Mg and Mg-based alloys for improving their hydrogen storage performances. In this paper, two technologies, viz. melt spinning and ball milling, were employed to fabricate the SmMg_(11)Ni alloy. The structure and hydrogen storage performance of these two kinds of alloys were researched in detail. The results reveal that the as-spun and milled alloys both contain nanocrystalline and amorphous structures. By means of the measurement of PCT curves, the thermodynamic parameters of the alloys prepared by MS and BM are ΔN_(Ms)(des) = 82.51 kJ/mol and ΔH_(BM)(des) = 81.68 kJ/mol, respectively, viz.ΔH_(MS)(des) ΔH_(BM)(des). The as-milled alloy shows a larger hydrogen absorption capacity as compared with the as-spun one. The as-milled alloy exhibits lower onset hydrogen desorption temperature than the as-spun one. As to the as-milled and spun alloys, the onset hydrogen desorption temperatures are557.6 and 565.3 K, respectively. Additionally, the as-milled alloy shows a superior hydrogen desorption property than the as-spun one. On the basis of time that required by desorbing hydrogen of 3 wt% H_2, the as-milled alloy needs 1488.574,390 and 192 s corresponding to hydrogen desorption temperatures 593,613,633 and 653 K, while the as-spun alloy needs 3600,1020,778 and 306 s corresponding to the same temperatures. The dehydrogenation activation energies of the as-milled and spun alloys are 100.31 and105.56 kJ/mol, respectively, the difference of which is responsible for the much faster dehydriding rate of the as-milled alloy.     

Twinning,phase boundary structure and development of high coercivity in Fe-rich Sm2Co17-type magnets

The microstructure of twinning as well as the phase boundary between 1:5 H and 2:17 R phase in Fe-rich Sm₂Co₁₇-type magnets was characterized at atomic scale using nanobeam diffraction and highresolution STEM-HAADF imaging,and the reason for the dramatic increase of coercivity during slow cooling was investigated based on the microchemistry analysis.The twinning relationship in the 2:17 R phase originates from ordered substitution of Sm atoms by Co-Co atomic pairs on every three(3033)and(3033)planes,leading to formation of two corresponding equivalent twin variants.The basal plane of the 2:17 R phase,the 1:3 R platelet phase across the 2:17 R cell and the 1:5 H cell boundary phase between two adjacent 2:17 R cells all can act as effective twin boundary.The cell boundary phase is precipitated along the pyramidal habit plane,and a fully coherent phase boundary(PB)is formed between the 1:5 H and 2:17 R phases with the orientation relationship to be PB//(1121)1:5 H//(1011)₂:17 R.The phase boundary may either be parallel to or intersect with the pyramidal planes occupied by Co-Co atomic pairs.The substantial increase of coercivity during slow cooling is ascribed to the development of large gradient of the elements concentration within the cell boundary phase,resulting in large gradient of domain wall energy,and thus the pinning strength of the cell boundary phase against magnetic domain wall motion is significantly enhanced.     

A hybrid coercivity mechanism for exchange-coupled nanocomposite permanent magnets

We propose a hybrid coercivity mechanism for exchange-coupled hard/soft multilayers, which incorporates elements of both the traditional nucleation and pinning mechanisms based on both threedimensional(3 D) and one-dimensional(1 D) micromagnetic calculations. The magnetic reversal starts with the nucleation of the domain wall near the defects or soft phases, which ends by the pinning usually in the same place. Therefore, pinning near the nucleation centers are the dominant coercivity mechanism for both exchange-coupled nanocomposites and so-called single-phased permanent magnets. Our proposed coercivity mechanism and calculated results agree very well with available experimental data,especially the recently reported high energy products achieved in NdFeB and SmCo based hard/soft multilayers. The hybrid coercivity mechanism can be readily extended to single-phased permanent magnets with defects and other magnetic systems.     

Magnetic properties and magnetization mechanism of anisotropic NdFeB/SmFeN hybrid bonded magnets prepared with different coercivity NdFeB powders

Anisotropic NdFeB/SmFeN hybrid bonded magnets were prepared by warm compaction process under an orientation magnetic field of 22 kOe,mixing with anisotropic SmFeN powders in different addition and HDDR-NdFeB powders in different coercivity.With the addition of 20 wt% SmFeN,the density and remanence of hybrid magnets increase from 5.58 g/cm³,8.4 kGs to 6.02 g/cm³,9.0 kGs,respectively.And as the addition amount of SmFeN powders varies from 20 wt% to 40 wt%,the maximum energy ...     

Influence of Pr-Al-Co alloy diffusion source on magnetic properties and microstructure of sintered Nd-Fe-B magnets processed by grain boundary diffusion

In this study, the influence of the content of Al and Co in the diffusion source on the magnetic performance and microstructure of the diffused magnet was studied by grain boundary diffusion treatment with Pr₇₀Al_30–xCo_x (x = 0 at%, 10 at%, 15 at%, 20 at%, 30 at%) alloys. When the Co content in the diffusion source increases from 0 at% to 10 at%, the coercivity enhancement in the Pr₇₀Al₂₀Co₁₀ diffused magnet is the highest, increased from 1.62 to 2.24 T, higher than 2.01 T of the Pr₇₀Al₃₀ diffused magnet. With further increase of Co content in the diffused source, the coercivity of the diffused magnet decreases gradually, the coercivity of Pr₇₀Al₁₅Co₁₅, Pr₇₀Al₂₀Co₁₀ and Pr₇₀Co₃₀ diffused magnet is 2.15, 1.99 and 1.81 T, respectively. Microstructural analysis shows that plenty of continuous grain boundary phases (CGBPs) can be formed in the Pr₇₀Al₂₀Co₁₀ diffused magnet under the synergistic effect of Al and Co, which leads to the enhancement of magnetic isolation between more adjacent grains. However, the amount of CGBP in the diffused magnets gradually decreases with the further increase of Co content in the diffusion source.     

Gaseous hydrogen storage properties of Mg-Y-Ni-Cu alloys prepared by melt spinning

For purpose of promoting the hydrogen absorption and desorption thermodynamics and kinetics properties of Mg-Ni-based alloys, partially substituting Y and Cu for Mg and Ni respectively and melt spinning technique were applied for getting Mg_(25-x)Y_xNi_9 Cu(χ = 0-7) alloys. Their microstructures and phases were characterized with the help of X-ray diffraction and transmission electron microscopy. Their hydrogen absorbing and desorbing properties were tested by a Sievert apparatus, DSC, and TGA, which were connected with a H_2 detector. In order to estimate the dehydrogenation activation energy of alloy hydride, both Arrhenius and Kissinger methods were applied for calculation. It is found that their hydriding kinetics notably declines, however, their hydrogen desorption kinetics conspicuously improves, with spinning rate and Y content increasing. Their hydrogen desorption activation energy markedly decreases under the same constraint, and it is found that melt spinning and Y substituting Mg improve the real driving force for dehydrogenation. As for the tendency of hydrogen absorption capacity,it presents an elevation firstly and soon after a decline with the rising of spinning rate, however, it always lowers with Y content growing. With Y content and spinning rate increasing, their thermodynamic parameters(△H and △S absolute values) visibly decrease, and the starting hydrogen desorption temperatures of alloy hydrides obviously lower.     

Magnetic properties and microstructure of nanocrystalline bulk Nd-Fe-B with Ce-Co addition

The influence of Ce-Co alloy addition and sintering holding time on permanent magnetic properties and micro structure of nanocrystalline Nd-Fe-B bulk alloy were investigated.The coercivity of Nd-Fe-B bulk alloy can be enhanced greatly by more than 100% after adding Ce-Co powders.However,when the concentration of Ce-Co is up to 30 wt%,the density of the magnet can reach the maximum value of 7.58 g/cm~3,but the coercivity does not increase significantly.On the other hand,with the increase of holding time to 10 min,the density and coercivity of magnets increase gradually,reaching up to 7.55 g/cm~3 and 1134.3 kA/m,respectively.After the addition of Ce-Co alloy,Ce-Co may easily diffuse into the Nd-Fe-B matrix during hot-pressing and under the high pressure and temperature,thus increasing the content of grain boundary phase and the pinning effect of grain boundary,which leads to the increase of coercivity.The extension of the hot-pressing holding time may be more conducive to the diffusion of CeCo into the Nd-Fe-B matrix.In addition,the effect of Ce-Co addition on the magnetic properties of Nd-FeB with different content of rare earth was also studied.The addition of Ce-Co can effectively increase the coercivity of nanocomposite Nd_2 Fe_(14)B/α-Fe magnets.The addition of Nb to the parent alloy can further improve the coercivity.For Nd_(11)Fe_(81.5)Nb_1 Ga_(0.5)B_6 alloy with 10 wt% Ce-Co addition,the coercivity can increase from 740.28 to 1098.48 kA/m.     

Simultaneous increase in remanence and coercivity during grain refining of Nd-Fe-B deformed magnets

To explore the feasibility of deep grain-size refinement in overcoming the problem of traditional B_r-H_ci trade-off in bulk permanent magnets, the effect of deformation temperature on the texture strength, grain refining, and magnetic properties of slow-deformed Nd-Fe-B magnets was systematically studied. As a result, strong textures with gradual grain refining from conventionally large size of D_L = 650 nm to small nanoscale size of D_L = 53 nm (D_L denotes the lateral size of the aligned plate-like grains) are observed as the temperature reduces from T_d = 650 °C to T_d = 450 °C. Moreover, magnetic observations show a simultaneous increase in remanence and coercivity as the grain refines from D_L = 650 nm to D_L = 127 nm. The increase in coercivity results from the grain size refinement as well as the smaller aspect ratio of the plate-like grains, and the increase in remanence results from the improved texture homogeneity. As compared with the D_L = 650 nm magnets, the simultaneous increase in remanence and coercivity leads to optimum enhancements of 57% in coercivity, 10% in remanence, and 25% in energy product, which demonstrate the feasibility of near-nanoscale grain refinement in overcoming the traditional B_r-H_ci trade-off for improved (BH)_max values. The failure of higher coercivities in the D_L ≤ 80 nm magnets is closely related with the defect effects of the grain boundaries. Mechanisms explaining the grain refining and texture changing behavior were also discussed.     

Recycled Nd-Fe-B sintered magnets prepared from sludges by calcium reduction-diffusion process

Environmental friendly recycling process for Nd-Fe-B sintered magnet sludges generated in the manufacturing process, which contain large amount of rare earth, including Nd, Pr and Dy, is badly needed so far. In present study, we have developed an effective route to obtain recycled sintered magnets from Nd-Fe-B sintered magnet sludges by calcium reduction-diffusion (RD) process. Compared to conventional recycling process, our research is focused on recovering most of the useful elements, including Nd, Pr, Dy, Co, and Fe together instead of just rare earth elements. To improve the recycling efficiency and reduce pollution, the co-precipitating parameters were simulated and calculated using MATLAB software. Most of useful elements were recovered by a co-precipitation method, and the obtained composite powders were then directly fabricated as recycled Nd-Fe-B powders by a calcium reduction-diffusion (RD) method. The recovery rates are 98%, 99%, 99%, 93%, and 99%, for Nd, Pr, Dy, Co, and Fe, respectively. The amount of useful elements contained in the recovered composite powders is greater than 99.71 wt%. The process of RD for synthesizing Nd₂Fe₁₄B and subsequently removing CaO was thoroughly investigated. Furthermore, the recycled Nd-Fe-B magnet exhibits a remanence of 1.1 T, a coercivity of 1053 kA/m, and an energy product of 235.6 kJ/m³, respectively, indicating that recycled Nd-Fe-B sintered magnet was successfully recovered from the severely contaminated sludges via an effective recycling route.     

Microstructure improvement related coercivity enhancement for sintered NdFeB magnets after optimized additional heat treatment

The microstructure, especially the Nd-rich phase and the grain boundary, in sintered NdFeB magnets plays an important role in magnetic reversal and coercivity mechanism. To better understand the effects of the microstructure on the coercivity, we investigated the microstructure and properties improvements of a commercial sintered NdFeB magnet after optimized additional heat treatment. The coercivity is enhanced from 1399 to 1560 kA/m. This enhancement has been explained in terms of the evolution of the grain boundary structure, and the formation of continuous thin layers of Nd-rich phase is important for high coercivity. The micromagnetic simulation together with the numerical analysis based on the nucleation model suggest that the reversed magnetic domains nucleate mainly at the interface of multi-junctions of Nd₂Fe₁₄B grains with high stray fields during the demagnetization process. Both improved anisotropy fields at grain boundaries and reduced stray fields at multi-junction Nd-rich phases contribute to the coercivity enhancement. This work has importance in understanding the crucial microstructure parameters and enhancing the obtainable properties for sintered NdFeB magnets.     

Structure and electrochemical hydrogen storage behaviors of Mg-Ce-Ni-Al-based alloys prepared by mechanical milling

The influences of milling time and Ce content on the electrochemical property and micro structure of asmilled Mg_(1-x)Ce_xNi_(0.9)Al_(0.1)(x=0,0.02,0.04,0.06,0.08)+50 wt%Ni alloys were investigated systematically.The as-milled alloys have an outstanding activation property.The cycle stability conspicuously grows up with milling time and Ce proportion increasing.The capacity retention rate at 100 th cycle of x=0.02 alloy augments from 47% to 63% when prolonging milling time from 5 to 30 h and it grows from55% to 82% for the 30 h milled alloy with Ce content growing from 0 to 0.08.The discharge capacity of x=0.02 alloy grows up invariably with milling time prolonging,while that of the 30 h milled alloys has the maximal value of 578.4 mAh/g with Ce content increasing.Moreover,the electrochemical kinetic properties of alloys significantly improve with milling duration extending,while they have the maximal values with Ce proportion varying.     

Effect of heterogeneous microstructure on magnetization reversal mechanism of hot-deformed Nd-Fe-B magnets

The hot-deformed(HD) Nd-Fe-B magnets show heterogeneous microstructure composed of coarse and fine grain regions. It is significant to fully understand the influence of this complex microstructure on the magnetization reversal process which can give the guidance for the enhancement of the magnetic properties. In this paper, the heterogeneous microstructure of the(HD) Nd-Fe-B magnets were characterized from the morphology, size, macro-texture and micro-structure. In addition, the magnetization reversal process of the HD Nd-Fe-B magnets was systematically analyzed by magnetic measurement, insitu domain evolution observation and micromagnetic simulation. The results indicate that the HD NdFe-B magnets mainly consist of fine grain regions(FGRs) and coarse grain regions(CGRs). The FGRs show plate-like grains with fine grain size and strong c-axis texture, while the CGRs show equiaxial grains with large grain size and weak c-axis texture. In particular, it is worth noting that the texture in homogeneity exists not only between FGRs and CGRs, but also inside both the FGRs and CGRs. The dominant coercivity mechanism of the HD Nd-Fe-B magnets is domain wall pinning. Also, the experimental analysis shows that the reverse domain is formed and expanded in the CGRs at low reverse applied field, while the reverse domain occurs in the FGRs at higher reverse applied field. The micromagnetic simulation results also confirm the above magnetization reversal process. In addition, micromagnetic simulation results also show that the orientation of the grains also affects the pinning strength, besides the grain size.     

Effect of cobalt substitution on magnetic properties and microstructure of nanocrystalline （NdDyTb）12.3（FeZrNbCu）81.7B6.0 ribbons

Effect of Co substitution and annealing treatment on the formation, magnetic properties and microstructure of (NdOyTb)12.3(FeZrNbCu)81.7CoxB6(x=0-15) ribbons prepared by rapid quenching and subsequent annealing was systematically investi-gated by means of differential scanning calorimeter (DSC), X-ray diffraction (XRD), high resolution scanning electron microscopy (HRSEM) and vibrating sample magnetometer (VSM). Phase analysis revealed single-phase material. The remanence polarization Jr and maximum en-ergy product (BH)max increased with increasing x from 0 to 12 and then decreased for x=lS. The intrinsic coercivity Hci of (NdDyTb)12.3 (FeZrNbCU)81.7-xCoxB6 ribbons optimally processed decreased from 1308.7 kA/m for x=0 to 817.4 kA/m for x=15. Optimum magnetic properties with Jr=1.041 T, Hci=944.9 kA/m and (BH)max=155.1 kJ/m3 were achieved by annealing melt-spun ribbon (x=-12) at 675℃ for 10 min. There was no significant influence of Co substitution on microstructure.     

Effects of grain boundary diffusion process on magnetic properties enhancement and microstructure evolution of hot-deformed Nd-Fe-B magnets

Grain boundary diffusion(GBD) process is an important approach for producing Nd-Fe-B magnets with high coercivity and high thermal stability.The GBD for hot-deformed Nd-Fe-B magnets with nanocrystalline micro structure is more complicated compared to sintered magnets.Here,we investigated the effects of different GBD methods,i.e.,intergranular addition(in-situ GBD 1#),in-situ GBD from magnet surface during hot pressing and hot deformation(in-situ GBD 2#),and conventional GBD,on the magnetic prope...     

Improved corrosion resistance and thermal stability of sintered Nd-Fe-B magnets with holmium substitution

The effects of Ho substitution for Nd on the microstructure, corrosion resistance and thermal stability of the Nd-Fe-B magnets were investigated. The(Nd,Ho)-O phase was formed with increasing Ho substitution. The results of potentiodynamic polarization and highly accelerated stress test show improved corrosion resistance with increasing Ho substitution. The optimum mass loss 0.29 mg/cm~2 is achieved.Moreover, the average temperature coefficients for remanence and coercivity in the range of 25-150℃are both closer to zero, indicating improved thermal stability. The mechanisms for the improved corrosion resistance and thermal stability are discussed in relation to the microstructure featuring the(Nd,Ho)-O phase.     

Optimization of both coercivity and knee-point magnetic field of Sm2Co17-type magnets via solid solution process

It is confirmed that phase homogenization is very important for improving the magnetic properties of 2:17-type Sm–Co sintered magnets. In this work, the influence of solid solution process on microstructure and magnetic properties of the Sm(Co_balFe_0.233Cu_0.073Zr_0.024)_7.6 sintered magnets was systematically studied. With the solid-solution treating duration (t_s) increasing from 0 to 4 h, intrinsic coercivity (H_cj) increases from 12.83 to 36.54 kOe, magnetic field at knee-point (H_knee) increases from 2.76 to 19.14 kOe, and the maximum energy product increases from 19.79 to 29.48 MGOe. The electron probe microanalyzer results reveal that there mainly exist gray and dark regions besides “white” rare earth-rich phase, and the content of Sm, Fe and Cu elements for the two kinds of regions changes a lot for the specimens. Furthermore, with t_s increasing up to 4 h, the elements content deviation between the gray and dark regions becomes small gradually from 3.94 at% to 0.27 at%, 7.66 at% to 0.21 at% and 7.27 at% to 0.16 at% for Sm, Fe and Cu elements, respectively. Moreover, transmission electron microscopy results show that the distribution of cell size is much more concentrated for aged specimens when t_s is 4 h. It is also found that the Cu concentration at cell boundaries for the 4 h solid-solution treatment case shows relatively higher values and greater concentration gradient (1.94 at%/nm). It is verified that sufficient solution treatment duration is prerequisite to form these homogeneous microstructural features, which are the key points for obtaining both high H_cj and H_knee.     

Effect of yttrium substitution on magnetic properties and service performances of Nd-Fe-B sintered magnets

We successfully fabricated partial Y substituted NdY-Fe-B magnets with nominal compositions of(Nd_1-xY_x)_13.80Fe_ba1Al_0.24Cu_0.1B_6.04(at%,x=0,0.1,0.2,0.3,0.4) by powder metallurgy process and the magnetic properties as well as service performances of the magnets were also systematically investigated.The phase constituents of the magnets have no obvious variation within the whole range of Y content,while the main phase grain...