Phase formation and magnetic properties of Nd2Fe14B-type Nd16Co76B8−xCx alloys and their hydrides

An attempt is made to synthesize Nd₂Co₁₄C compound by mechanical alloying Nd₁₆Co₇₆B_8−xC_x (0x8) alloys and subsequent annealing. Phase formation and magnetic properties of Nd₂Fe₁₄B-type Nd₁₆Co₇₆B_8−xC_x alloys and their hydrides are investigated. The Nd₂Co₁₄(B,C) phase with Nd₂Fe₁₄B-type structure is formed for Nd₁₆Co₇₆B_8−xC_x (0x7) alloys, while NdCo₇C_δ phase with TbCu₇-type structure is observed in Nd₁₆Co₇₆C₈ alloy. The lattice parameter c of the Nd₂Co₁₄(B,C) phase decreases with increasing the carbon content. A limit volume of the unit cell to form the Nd₂Fe₁₄B-type structure is estimated to be 0.870 nm³. The spin-reorientation temperature T_SR increases with increasing the carbon content, due to an enhancement of magnetocrystalline anisotropy caused by carbon substitution for boron. After hydrogenation, the lattice expansion is observed for Nd₁₆Co₇₆B_8−xC_x (0x7) alloys. The spin-reorientation temperature of Nd₁₆Co₇₆B_8−xC_xH_y (0x7) is much lower than that of the host alloys. Some structural and magnetic properties of hypothetic Nd₂Co₁₄C and Nd₂Co₁₄CH_y compounds are estimated by extrapolation.     

Cobalt substituted R---Fe(Co)---C alloys

The formation of tetragonal R₂(FeCo)₁₄C phase has been examined in as-cast and melt-spun R₁₄Fe_78−xCo_xC₈ alloys with cobalt substitutions (R = Y, Dy, Nd). The magnetic properties over a temperature range and the microstructure have been studied as a function of cobalt content. The Curie temperature is increased with Co content but the anisotropy K is decreased. High cobalt content leads to the formation of 1:5 phase. High corecivities have been developed in as-cast and melt-spun Dy₁₄Fe_78−xCo_xC₈ alloys with Co content at zero and 32 at %, respectively. As-cast Nd₁₆Fe_78−xCo_xC₈ alloys did not show any permanent magnetic properties although they had the 2:14:1 phase. However, melt-spun and powdered Nd---Fe---Co---C samples showed a coercivity with the highest value corresponding to a melt-spun Nd₁₄Fe₇₈C₈ sample. Microstructure studies showed that the high H_C in ribbons is due to the fine grain size which is in the range of 500–1000 Å.     

Enhanced magnetic properties of Nd–Fe–B thin films crystallized by heat treatment

Nd₂Fe₁₄B Φ phase crystallites were formed in Nd_16.7Fe_65.5B_17.8 thin films prepared by RF sputtering with subsequent heat treatment. The 2 μm-thick films were deposited onto 0.1 mm Mo sheets at an average substrate temperature (T_s) of 365°C. The enhanced magnetic properties of the magnetically anisotropic thin films were investigated using different heating rates (h_r) of 10°C, 20°C, 50°C and 100°C/min in an annealing experiment. Transformation from the amorphous phase to the crystalline phase is clearly manifested by the formation of fine crystallites embedded as a columnar matrix of Nd₂Fe₁₄B phase. High-resolution scanning electron microscope data of the cross-section of the annealed films show columnar stacking of Nd₂Fe₁₄B crystallites with sizes <500 nm. Transmission electron microscope observations revealed that the microstructure of these films having out-of-plane magnetization consists of uniformly distributed Φ phase with grain size around 400 nm together with small Nd rich particles. This grain size of Φ phase is comparable to the single domain particle diameter of Nd₂Fe₁₄B. Significant change in _iH_c, 4πM_r and 4πM_s with h_r was confirmed. Annealing conditions with a heating rate of 50°C/min to an annealing temperature (T_a) of 650°C for 30 min was consequently found to give optimum properties for the NdFeB thin films. The resulting magnetic properties, considered to be the effect of varying h_r were _iH_c= 1307–1357 kA/m, 4πM_r=0.78–1.06 T and 4πM_s=0.81–1.07 T.     

Effect of Ti and C additions on structural and magnetic properties of (Pr,Nd)–Fe–B nanocrystalline magnetic materials

Effects of titanium carbide (TiC) addition on structural and magnetic properties of isotropic (Pr,Nd)–Fe-B nanocrystalline magnetic materials have been investigated. In this work, we investigate the effect of TiC addition on a (Pr,Nd)-poor and B-rich composition, as well as on a B-poor and (Nd,Pr)-rich composition. Rapidly solidified (Pr,Nd)–Fe–B alloys were prepared by melt-spinning. The compositions studied were (Pr_1−xNd_x)₄Fe₇₈B₁₈ (x=0, 0.5, and 1) with addition of 3 at% TiC. Unlike the (Pr_xNd_1−x)_9.5Fe_84.5B₆ materials that present excellent values for coercive field and energy product, the (Pr,Nd)-poor and B-rich composition alloys with TiC addition present lower values. Rietveld analysis of X-ray data and Mössbauer spectroscopy revealed that samples are predominantly composed of Fe₃B and -Fe. For the RE-rich compositions (Pr_xNd_1−x)_9.5Fe_84.5B₆ (x=0.1, 0.25, 0.5, 0.75, and 1) with the addition of 3 at% TiC, the highest coercive field and energy product (8.4 kOe and 14.4 MGOe, respectively) were obtained for the composition Pr_9.5Fe_84.5B₆.     

非晶Nd3Fe81B16合金的晶化及其对磁性和M?ssbauer谱的影响

本文报道利用单辊方法制备的非晶Nd₃Fe₈₁B₁₆合金的晶化及其对磁性和M?ssbauer谱的影响。发现在非晶Fe₈₁B₁₉合金中用3at％Nd取代B,使非晶Fe₈₁B₁₉合金的晶化温度提高88℃。在适当的退火条件下晶化后样品在室温下的磁性是:σ_s=189emu/g,σ_r/σ_s=0.7,_iH_c=2.15kOe,B_r≈12kG,_bH_c=2kOe,(BH)_max≈8MGOe。与目前广泛使用的六角铁氧体相比,_bH_c相近,但B_r和(BH)_max远比六角铁氧体高。这种材料仅含有少量的Nd,因此可能开发为一种新的廉价永磁材料。本文对少量Nd的添加对非晶FeB合金的晶化温度,磁性和M?ssbauer谱的影响进行了讨论。初步探讨了高矫顽力的来源,认为它的磁化和反磁化过程可以用畴壁钉扎理论解释。 关键词：     

The dissolution kinetics of free iron in Nd-Fe-B permanent magnet alloys

Three kinds of NdFeB alloys, near the Nd₂Fe₁₄B ( φ phase ) composition of the Fe-(Nd₂B) pseudobinary phase diagram, were used to study the kinetics of free iron dissolution in the matrix, which is extremely important for the attainment of high coercivity. The dissolution equations together with the time exponent, n( , ) and activation energies of rate constants, Q(34–40.9 kcal/mol) were derived. These indicate that the quantity of Nd-rich liquid phase plays an important role in the dissolution kinetics. For the ‘hypo-φ’ composition (Fe-rich), grain boundary diffusion dominates. For φ and ‘hyper-φ’ (Nd-rich) composition, interface reaction dominates. The low activation energies of this system are attributed to the activated effect of φ phase formation and liquid phase assisted grain boundary diffusion, it is found that there will be no free iron left after powder pulverizing and sintering of the commercial Nd₁₅Fe₇₇B₈ alloy.     

Magnetic properties and spin reorientation of iron rare earth based intermetallics

The Curie temperature and saturation magnetization M_s(μ_B/f.u.) of R₂Fe₁₄B have been discussed. The spin reorientations of Nd₂Fe₁₄B compounds have been studied by many authors with various methods, but have not been checked with the neutron diffraction method. We investigated the spin reorientation of Nd₁₅Fe₇₈B₇ by neutron diffraction and obtained θ = 26°34' at 77 K which is in good agreement with other authors' results. The small amount substitution of Si for Fe in Nd₂(Fe_1−xSi_x)₁₄B increases T_c and _cH_c of the compound. These will be able to make an advantage for Nd-Fe -B magnets.     

Magnetic characteristics of R2(Fe, Co)14B systems (R = Y, Nd and Gd)

R₂(Fe, Co)₁₄B compounds (R = Y, Nd and Gd) were prepared in high purity. The magnetic behavior of R₂(Fe, Co)₁₄B compounds is reported over the temperature range 4 to 300 K. The effects of Fe substitution by Co on the saturation magnetization, Curie temperature and anisotropy are presented. The spin-reorientation temperature is lowered as Co replaces Fe. This also results in a reduced cone angle.

The R₂Fe_14−xCo_xB alloys crystallize in the tetragonal structure over the entire concentration range of 0 x 14. When Fe is substituted by Co, the Curie temperature increases significantly, the saturation magnetization increases to a maximum value around x = 2, and the anisotropy becomes planar for R = Y and Gd. The Nd₂(Fe, Co)₁₄B systems all exhibit uniaxial anisotropy at room temperature and Nd₂Co₁₄B is strongly uniaxial at 77 K. The Nd₂(Fe, Co)₁₄B systems are conical at 77 K.     

Coercivity mechanism in nanophase (Nd–Pr)–Fe–B melt spun alloys

The nucleation mechanism to predict coercivity values in melt-spun exchange-coupled (Nd_1−xPr_x)_yFe_94−yB₆ alloys for various Nd:Pr ratios x, and Fe:RE ratios y, was tested using the dependence of the anisotropy constant K₁ on Pr content x for the minimum nucleation field H_N^min in the modified Brown's equation. Very good agreement was found between experimental data and theoretical values, confirming the predominance of the nucleation of reverse domains over the wall pinning process in the coercivity mechanism of melt spun REFeB alloys.     

质子辐照对永磁合金微观结构演化的研究

钐钴和钕铁硼稀土永磁合金已经广泛应用于粒子加速器的波荡器和其他器件中,作为加速器的重要组成部分,永磁合金在辐照环境中长期服役会出现磁性能损失的现象,这会影响束流的品质.为了探讨产生这个现象的微观机理,采用透射电镜对质子辐照前后的钐钴和钕铁硼稀土永磁合金进行了微观结构演化的表征和分析,统计了由辐照析出的纳米晶体积密度和粒径分布,并讨论了微观结构演化对宏观磁性能损失的影响.结果表明,随着质子辐照损伤程度的增加,永磁合金的微观结构从单晶结构转变为纳米晶多晶结构,且纳米晶和基体的晶体结构相同.钕铁硼的纳米晶体积密度先增大后减小,粒径分布先增大后不变;钐钴的纳米晶体积密度逐渐减小,粒径逐渐增大.在2 dpa的质子辐照损伤程度下,钕铁硼稀土永磁合金比钐钴永磁合金的非晶化趋势更明显.     

Thermal-expansion anomalies and spontaneous magnetostriction of Lu2Fe17−xSix intermetallic compounds

The thermal expansion of Lu₂Fe_17−xSi_x solid solutions has been measured by X-ray powder diffraction. The magnetic ordering in all compounds within the homogeneity range (x3.4) is accompanied by a large spontaneous volume magnetostriction, distributed anisotropically over the principal axes of the hexagonal crystal structure. The volume effect ω_s in the ground state reaches 14.7×10⁻³ in Lu₂Fe₁₇ and decreases monotonously to 8.9×10⁻³ for x=3.4, following the reduction of magnetic moment. Despite a still large ω_s, the Invar behavior observed in Lu₂Fe₁₇ changes to a positive thermal expansion for x>1 due to an increasing Curie temperature.     

Influence of structure on coercivity in nanocrystalline (Fe1−xCox)86Hf7B6Cu1 alloys

The relationship between coercivity and structure in nanocrystalline (Fe_1−xCo_x)₈₆Hf₇B₆Cu₁ (x=0–1) alloys was surveyed. It was found that the increase of Co content in the alloys studied was accompanied by the increase of coercivity. However, we suggest that the factors influencing the coercivity change with the concentration of cobalt in these nanocrystalline alloys. In the iron-rich alloys, the average grain size and magnetostriction play predominant roles in the coercivity. On the other hand, in the case of cobalt-rich alloys, the coercivity mostly originates from the FCC-Co phase with large magnetocrystalline anisotropy and the weak exchange coupling between BCC-Fe(Co) and FCC-Co(Fe).     

MAGNETIC PROPERTIES AND CRYSTALLIZATION OF THE RAPIDLY QUENCHED (Fe1-xNdx) 81.5B18.5 ALLOYS

Magnetic properties and crystallization behaviors of amorphous (Fe_1-xNd_x) _81.5B_18.5 alloys were studied. The crystallization temperature is found to rise at first and then drop monotonically with x, having a maximum value of 976K at x=0.11 (9at% Nd). The (Fe_1-xNd_x) _81.5B_18.5 alloys prepared at a quenching rate of v_s = 6.6m /s are amorphous, and exhibit good glass formability. Both the coercive field H_c and energy product (BH)_max depend strongly on Nd concentration. Amorphous (Fe_1-xNd_x) _81.5B_18.5 alloys with higher Nd concentration have a high coercive field at low temperature, due to the large random uniaxial anisotropy of Nd. The room-temperature H_c and (BH)_max obtained on optimal annealing con-ditions show two maxima as a function of Nd concentration x. The highest room-temperature coercive field H_c =22 kOe within the Nd concentrations around x=0.368 and the maximum energy product(RH)_max= 13.3 MG·Oe at x =0.055 are observed. The hard magnetic properties of these crystallized samples are related to the presence of the bard magnetic Nd₂Fe₁₄B phase.     

Low-field magnetoresistance of Ag-substituted perovskite-type manganites

A series of bulk polycrystalline Nd_1−xAg_xMnO₃ samples were prepared by conventional solid-state reaction processing, for x between 0.1 and 0.5. The structure, magnetism, and magnetoresistance (MR) of the samples are investigated. The X-ray diffraction patterns show that the x=0.1 sample is a single perovskite structure, while x0.167, samples consist of a ferromagnetic perovskite phase and two nonmagnetic phases, Ag and Mn₃O₄. The MR of Nd_1−xAg_xMnO₃ is enhanced by increasing the composition of Ag. Compared with the sample of x=0.1, the x=0.5 sample has a significantly larger value of low-field MR. The enhanced low-field MR is related to the spin-dependent scattering of spin-polarized electrons at the interfaces between the perovskite grains and silver granules.     

FORMATION AND MAGNETIC PROPERTIES OF NEW COMPOUNDS R3Fe29-xCrx(R=Y,Ce,Nd,Sm,Gd,Tb,and Dy)

A systematic investigation of structure and magnetic properties of the new R₃Fe_29-xCr_x compounds(R=Y,Ce,Nd,Sm,Gd, Tb,and Dy)has been performed. The Curie temperature of R₃Fe_29-xCr_x increased with increasing atomic number fromR=Ce to Gd and de creased from Gd to Dy. The saturation magnetization of R₃Fe_29-xCr_x at 4.2 K decreased gradually with increasing atomic number from R=Y to Dy,except for Ce. The spin reorientations of the easy magnetization d irection were observed at around 230 K for Nd₃Fe_24.5Cr_4.5 and 180 K for Tb₃Fe_28.0Cr_1.0,and the magnetohistory effects were obser ved for Nd₃Fe_24.5Cr_4.5 and Sm₃Fe_24.0Cr_5.0 in a low field of about 0.04 T. First order magnetization process occurs in magnetic field of around 2.3 T at room temperature for Tb₃Fe_28.0Cr_1.0. The saturation magnetization of Y₃Fe_27.2Cr_1.8 at 4.2 K is 52.2μ_B/f.u., which corresponds to an average magnetic moment of 1.92μ_B per each Fe atom.     

NEUTRON-POWDER-DIFFRACTION STUDY OF THE STRUCTURE AND MAGNETIC PROPERTIES OF Nd2Fe14Si3

The crystal and magnetic structures of Nd₂Fe₁₄Si₃ at room temperature were refined by Rietveld analysis of neutron-powder-diffraction data. It was found that silicon atoms occupy preferentially both 18h and 18f of Th₂Zn₁₇-type structure with occupancies 0.36 and 0.14, respectively, The Fe-Fe bond-lengths computed with the refined crystallographic parameters have optimum values, as compared with those of Nd₂Fe₁₇ compounds, which can explain well why the Curie temperature rises strongly when the unit cell volume reduces with the substitution of silicon for iron in Nd₂Fe₁₇.     

Mn42Al50-xFe8+x合金的磁性和磁热效应

研究了Mn₄₂Al_50-xFe_8+x合金的结构、磁性和磁热效应. 通过成分调节, 居里温度T_C在室温附近一宽温区连续可调, 分别为270 K (Mn₄₂Al₄₂Fe₁₆), 341 K (Mn₄₂Al₄₀Fe₁₈)和370 K(Mn₄₂Al₃₈Fe₂₀). 磁化强度在相变温度处发生一陡降, 热磁曲线和等温磁化曲线均未观察到热和磁的滞后, 表明发生一可逆的二级相变. 在各自居里温度附近, 0-5 T的外磁场变化下磁熵变峰值分别为2.48, 2.52和2.40 J·kg^-1·K^-1. Mn_50-xAl_50-yFe_x+y合金的磁熵变峰值虽然与许多优良的磁制冷材料相比并不大, 但是制备该化合物的原材料价格非常低廉, 制备工艺简单, 加工成型也较容易, 化合物本身耐腐蚀性、延展性较好, 且在居里温度附近发生的是可逆的二级相变, 无晶格或结构的变化, 有利于制冷剂的多次循环使用. 关键词： 磁性 磁热效应 二级相变     

A NEUTRON POWDER DIFFRACTION STUDY OF THE STRUCTURE IN Nd2Fe17Nx(x = 2.5, 3.0, 5.5)

The crystallographic and magnetic structures of Nd₂Fe₁₇N_x(x = 2.5, 3.0, 5.5) at room temperature were refined by Rietveld analysis of neutron powder diffraction data. We found that Nd₂Fe₁₇N_x has a Th₂Zn₁₇ type structure (S.G. R3m) and the nitrogen atoms occupy both 9e and 18g sites simultaneously and at different rates.     

Study of the magnetic structure for Nd2Fe14B

The method of multi-ion crystal field calculation is applied to compute the magnetic structure of Nd₂Fe₁₄B. By means of fitting calculation, a set of crystal field coefficients, cone angle θ (32°) of spin direction and the temperature of spin reorientation T_sr (130 K) are obtained, which are in good agreement with experiment. The magnetic structure of the rate earth ion Nd is determined from the calculation.     

Temperature dependence of the electrical resistivity of amorphous Co80−xErxB20 alloys

The temperature dependence of the electrical resistivity of amorphous Co_80−xEr_xB₂₀ alloys with x=0, 3.9, 7.5 and 8.6 prepared by melt spinning in pure argon atmosphere was studied. All amorphous alloys investigated here are found to exhibit a resistivity minimum at low temperature. The electrical resistivity exhibits logarithmic temperature dependence below the temperature of resistivity minimum T_min. In addition, the resistivity shows quadratic temperature behavior in the interval T_min<T<77 K. At high temperature, the electrical resistivity was discussed by the extended Ziman theory. For the whole series of alloys, the composition dependence of the temperature coefficient of electrical resistivity shows a change in structural short range occurring in the composition range 8–9 at%.