Effects of underlayer materials and substrate temperatures on the structural and magnetic properties of Nd2Fe14B films

Thin films of Nd_2Fe_{14}B were fabricated on heated glass substrates by dc magnetron sputtering. Different material underlayers (Ta, Mo, or W) were used to examine the underlayer influence on the structural and magnetic properties of the NdFeB films. Deposited on a Ta buffer layer at 420℃, the 300 nm thick NdFeB films were shown to be isotropic. But when the substrate temperature T_s was elevated to 520℃, the Nd_2Fe_{14}B crystallites of (00l) plane were epitaxially grown on Ta (110) underlayer. In contrast, Mo (110) buffer layer could not induce any preferential orientation in NdFeB film irrespective of the substrate temperature or film thickness. The W buffer layer was found to be most effective for the nucleation of Nd_2Fe_{14}B crystallites with c-axis alignment perpendicular to the film plane when T_s<490℃. But at T_s=490℃ the magnetic layer became isotropic. The maximum coercivity obtained was about 995 kA/m for the 100nm film deposited on W underlayer at 490℃. These variations were tentatively explained in terms of the lattice misfit between the underlayer and the magnetic layer, combined with the considerations of underlayer morphologies.     

Sm3（F3,Co,Mn）29 compounds：promising materials for permanent magnets

The outstanding hard-magnetic properties are reported of Sm_3Fe_{28.1-x}Co_xMo_{0.9} compounds with x=12, 14, 16. In this alloy system, only a small amount of Mo is needed to stabilize the 3:29 structure so that the magnetic properties are not seriously affected by the presence of this nonmagnetic element. Substitution of Co for Fe leads to a significant increase of the magnetic anisotropy, and for x≥14 the easy magnetization direction changes from easy plane to the easy axis. In this alloy system, the compound Sm_3Fe_{12.1}Co_{16}Mo_{0.9} is a very promising candidate for permanent magnet applications. Its room temperature saturation magnetization (μ_0M_s=1.5 T) and anisotropy field (B_{an}=6.5 T) are comparable to the values for Nd_2Fe_{14}B (μ_0M_s=1.6 T and B_{an}=7 T). However, the Curie temperature of Sm_3Fe_{12.1}Co_{16}Mo_{0.9} is 1020 K, which is appreciably higher than that for Nd_2Fe_{14}B (T_C=588 K).     

焙烧条件对Ce离子价态影响的XPS研究

在均相沉淀法制备含铈化合物的过程中,利用XRD和IR尤其是XPS研究了含Ce化合物在不同焙烧温度条件下产物的结构、铈离子的价态变化、化合物表面性质及其内核电子构型。XRD结果表明,焙烧温度的不同可产生不同的铈基化合物,导致产物中Ce离子价态的变化,IR结果也证实了这一点。单纯均相沉淀法得到的产物为三价的斜方晶系的单晶Ce_2O(CO_3)_2·H_2O(Ⅲ)微粒;将三价的Ce_2O(CO_3)_2·H_2O加热到200℃,产物转化成高价态六价化合物CeO(CO_3)_2·H_2O(Ⅵ);加热温度再升高到250℃,产物转化为稳定的四价化合物CeO_2(Ⅳ)。XPS通过对3种不同价态化合物的O(1s),Ce(3d),Ce(4d)峰进行精细扫描,研究了产物的表面性质及其内部电子构型,比较结果证实了不同价态铈化合物的形成是由于内核价电子构型的差异引起的。     

Anisotropic nanocomposite soft/hard multilayer magnets

Experimental and theoretical researches on nanostructured exchange coupled magnets have been carried out since about 1988. Here, we review the structure and magnetic properties of the anisotropic nanocomposite soft/hard multilayer magnets including some new results and phenomena from an experimental point of view. According to the different component of the oriented hard phase in the nanocomposite soft/hard multilayer magnets, three types of magnets will be discussed:1) anisotropic Nd_2Fe_(14)B based nanocomposite multilayer magnets, 2) anisotropic SmCo_5 based nanocomposite multilayer magnets, and 3) anisotropic rare-earth free based nanocomposite multilayer magnets. For each of them, the formation of the oriented hard phase, exchange coupling, coercivity mechanism, and magnetic properties of the corresponding anisotropic nanocomposite multilayer magnets are briefly reviewed, and then the prospect of realization of bulk magnets on new results of anisotropic nanocomposite multilayer magnets will be carried out.     

晶粒大小分布对纳米晶磁体Pr2Fe14B剩磁和矫顽力的影响

用微磁学有限元法计算了纳米晶磁体Pr2Fe14B的退磁曲线，文中模拟了三种具有不同晶粒大小分布的样品。计算结果表明，剩磁增强与磁体的晶粒尺寸分布情况无关而依赖于平均晶粒直径。晶粒尺寸分布对矫顽力的影响与磁体中的晶间交换耦合作用密切相关。     

Clarifying the basic phase structure and magnetic behavior of directly quenched (Ce,La)2Fe14B alloys with various Ce/La ratios

To improve the performance/cost ratio of NdFeB based permanent magnets, Ce or/and La substitutions for Nd have been suggested. To better understand the effects of these substitutions, the fundamental behavior of (Ce,La)-Fe-B alloys has to be clearly understood. Here, we reported a systematic investigation on the phase structure, microstructure, and magnetic properties of melt-spun (Ce,La)₂Fe₁₄B alloys. The results confirm that partial substitution of Ce by La can effectively enhance the hard magnetism and thermal stability of (Ce_1-xLa_x)₂Fe₁₄B alloys, while over 80% La substitution leads to the decomposition of 2:14:1 phase. The lattice parameters a, c and the Curie temperature T_c of 2:14:1 phase increase linearly with the increasing La content. La substitution can effectively refine the grain, resulting in the enhancement of inter-grain exchange coupling. The (Ce_0.7La_0.3)₂Fe₁₄B alloy with a mean grain size of 25 nm exhibits high remanence, maximum energy product and intrinsic coercivity up to 0.69 T, 6.2 MGOe and 217 kA/m, respectively. The present work provides a good understanding on the melt-spun (Ce,La)-Fe-B system for further developing low cost rare earth permanent magnets.     

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.     

Multiple magnetic transitions in single crystals of Ce_(12)Fe_(57.5)As_(41) and La_(12)Fe_(57.5)As_(41)

Measurements of magnetic and transport properties were performed on needle-shaped single crystals of Ce_(12)Fe_(57.5)As_(41)and La_(12)Fe_(57.5)As_(41).The availability of a complete set of data enabled a side-by-side comparison between these two rare earth compounds.Both compounds exhibited multiple magnetic orders within 2-300 K and metamagnetic transitions at various fields.Ferromagnetic transitions with Curie temperatures of 100 and 125 K were found for Ce_(12)Fe_(57.5)As_(41)and La_(12)Fe_(57.5)As_(41),respectively,followed by antiferromagnetic type spin reorientations near Curie temperatures.The magnetic properties underwent complex evolution in the magnetic field for both compounds.An antiferromagnetic phase transition at about 60 K and 0.2 T was observed merely for Ce_(12)Fe_(57.5)As_(41).The field-induced magnetic phase transition occurred from antiferromagnetic to ferromagnetic structure.A strong magnetocrystalline anisotropy was evident from magnetization measurements of Ce_(12)Fe_(57.5)As_(41).A temperature-field phase diagram was present for these two rare earth systems.In addition,a logarithmic temperature dependence of electrical resistivity was observed in the two compounds within a large temperature range of 150-300 K,which is rarely found in 3D-based compounds.It may be related to Kondo scattering described by independent localized Fe 3d moments interacting with conduction electrons.     

Phase distribution and computed magnetic properties of high-remanent composite magnets

Numerical micromagnetic calculations using finite-element techniques allow a quantitative treatment of the correlation between the microstructure and the basic magnetic properties of two-phase permanent magnets such as the remanence, the coercive field and the maximum energy product. For the investigation of (A) the role of the amount of the soft magnetic phase, and (B) the effect of grain shape, realistic three-dimensional grain arrangements have been used. The numerical results show that both short-range exchange and long-range magnetostatic interactions determine the magnetic properties. The optimal microstructure of an isotropic nanocrystalline permanent magnet was found to consist of soft magnetic particles with a large spontaneous magnetization embedded between hard magnetic grains. Exchange interactions than enhance the remanence of isotropic, composite magnets of Nd₂Fe₁₄B and -Fe by about 60%. Because of exchange hardening the soft magnetic phase can be increased up to 50% without a significant loss of coercivity. A uniform grain structure suppresses strong demagnetizing fields and this increases coercivity by 30% as compared with irregular shaped particles.     

Er3(Fe,Co, M)29化合物(M=Cr,V, Ti,Mn, Ga,Nb)的结构与磁性

合成了Er_３Fe_29-x-yCo_xM_y化合物(M=Cr, V, Ti, Mn, Ga, Nb )并用x射线衍射和磁测量等手段研究了它们的结构和磁性. 发现Fe基Er_３(Fe,M)_２９化合物结晶成哑铃对Fe-Fe无序替代的Th₂Ni₁₇型结构(P6₃/mmc空间群)而不能形成Nd₃(Fe,Ti)_２９型结构，因此其化学式也可以用Er_2－n(Fe,M)_17+2n (n=0.2)表示. 当Er_３Fe₂₉化合物中部分Fe原子被M原子所取代时，其居里温度均有一定程度的提高. 所有Er_３(Fe,M)_２９化合物在室温均为易面型各向异性. 当Er_３(Fe,M)_２９ (M=Cr, V)中的部分Fe原子被Co原子取代且Co原子数与Fe原子数达到一定比值时，得到一个单斜结构的新相. 磁测量表明Er_３Fe_19.5Co₆V_3.5在室温可能为单轴各向异性，在162K出现自旋重取向，其各向异性由易轴型变为易面型. 在5K下于难磁化方向磁化时观察到一个一级磁化过程(FOMP). 关键词： 稀土金属间化合物 晶体结构 磁晶各向异性     

纳米复合永磁材料的有效各向异性与矫顽力

研究了纳米Nd2Fe14B/α-Fe复合永磁材料中晶粒交换耦合相互作用对有效各向异性的影响和变化规律.结果表明：晶粒之间的交换耦合作用使材料的有效各向异性Keff随晶粒尺寸的减小而下降、随软磁性相成分的增加而降低. 当晶粒尺寸 减小到4nm时，Keff值减小为其各自通常各向异性常数值的1/3—1/4.有效各向异性的变化特点与矫顽力的变化规律基本相同.纳米复合永磁材料矫顽力的降低主要由于有效各向异性的减小而引起. 关键词： 纳米复合永磁材料 交换耦合相互作用 有效各向异性 矫顽力     

Effect of post-sintering annealing on microstructure and coercivity of Al85Cu15-added Nd-Fe-B sintered magnets

Effects of post-sintering annealing on the microstructure and coercivity have been investigated for the Al₈₅Cu₁₅-added (Pr, Nd)_14.8Fe_78.7B_6.5 sintered magnets. It is found that the optimum annealing temperature at which the coercivity _iH_c reaches a maximum decreases from 550 °C for the magnets added with 0.3% and 0.6% Al₈₅Cu₁₅ to 480 °C for the magnets added with 0.9% and 1.2% Al₈₅Cu₁₅. The decrease in optimum annealing temperature is related to the precipitation of Al-Cu or (Pr, Nd)−Cu liquid phase among (Pr, Nd)-rich phases during annealing. Existence of Al-Cu or (Pr, Nd)−Cu liquid phase is beneficial to dissolve the irregularities of (Pr, Nd)₂Fe₁₄B grain interface and increase the quantities of (Pr, Nd)-rich phases at the grain boundary, thus optimizing the grain boundary microstructure. The modifications of the microstructure are helpful to decouple the exchange interaction between (Pr, Nd)₂Fe₁₄B hard magnetic grains, thereby increasing the coercivity.     

Nano-sized disorders in hard magnetic grains and their influence on magnetization reversal at artificial Nd/Nd2Fe14B interfaces

We have investigated the effect of lattice disorders near the surface of hard magnetic Nd₂Fe₁₄B grains on coercivity using artificial interfaces created by sputter depositing Nd on polished surface of Nd-Fe-B sintered magnets. The interfacial structure was manipulated by annealing the coated samples at 550 °C in vacuum with and without Ta cap. Nano-beam electron diffraction revealed a few nm thick disordered layer within the Nd₂Fe₁₄B phase at the Nd/Nd₂Fe₁₄B interface of a low coercivity sample, while a high coercivity sample showed a well-defined crystal structure of Nd₂Fe₁₄B near the NdO_x/Nd₂Fe₁₄B interface.     

Effects of dipolar interactions on the magnetic hyperthermia of Zn0.3Fe2.7O4 nanoparticles with different sizes

Tumor-targeted magnetic hyperthermia has recently attracted much attention.Magnetic nanoparticles(NPs) are heat mediator nanoprobes in magnetic hyperthermia for cancer treatment.In this paper,single cubic spinel structural Zn_0.3Fe_2.7O₄ magnetic NPs with sizes of 14 nm-20 nm were synthesized,followed by coating with SiO₂ shell.The SLP value of Zn_0.3Fe_2.7O₄/SiO₂ NPs below 20 nm changes non-monotonically with the concentration of solution under the alternating current(AC) magnetic field of 430 kHz and 27 kA/m.SLP values of all Zn_0.3Fe_2.7O₄/SiO₂ NPs appear a peak value with change of solution concentration.The solution concentrations with optimal SLP value decrease with increasing magnetic core size.This work can give guidance to the better prediction and control of the magnetic hyperthermia performance of materials in clinical applications.     

相分布和晶粒尺寸对Nd2Fe14B/ɑ-Fe纳米复合永磁材料矫顽力的影响

本文采用统计平均方法研究了软、硬磁性晶粒尺寸及相分布对Nd2Fe14B/α-Fe纳米复合永磁材料矫顽力的影响。计算结果表明：对于单相纳米硬磁材料，磁体矫顽力随着硬磁性晶粒尺寸的减小而降低；对于软、硬两磁性相组成的Nd2Fe14B/a-Fe纳米复合永磁材料，两相的随机分布将导致磁体矫顽力随硬磁性晶粒尺寸的减小呈现极大值。本文的计算结果还表明当硬磁性晶粒尺寸大于软磁性晶粒的最佳尺寸时(15nm)，具有多层膜结构的Nd2Fe14B/a-Fe纳米复合永磁材料将比两相随机分布时具有更大的矫顽力。     

Influence of Shell Formation on Morphological Structure,Optical and Emission Intensity on Aqueous Dispersible NaYF4:Ce/Tb Nanoparticles

A highly water-dispersible NaYF₄:Ce/Tb (core), NaYF₄:Ce/Tb@NaYF₄(core/shell) and NaYF₄:Ce/Tb@NaYF₄@SiO₂ (core/shell/SiO₂) nanoparticles (NPs) were synthesized via a general synthesis approach. The growth of an inert NaYF₄ and silica shell (~14 nm) around the core-NPs resulted in an increase of the average size of the nanopaticles as well as broadening of their size distribution. The optical band-gap energy slightly decreases after shell formation due to the increase the crystalline size. To optimize the influence of shell formation a comparative analysis of photoluminescence properties (excitation, emission, and luminescence decay time) of the core, core/shell, and core/shell/SiO₂ NPs were measured. The emission intensity was significantly enhanced after inert shell formation around the surface of the core NPs. The Commission International de l’Eclairage chromaticity coordinates of the emission spectrum of core, core/shell, core/shell/SiO₂ NPs lie closest to the standard green color emission at 545 nm. By quantitative spectroscopic measurements of surface-modified core-NPs, it was suggested that encapsulation with inert and silica layers was found to be effective in retaining both luminescence intensity and dispersibility in aqueous environment. Considering the high aqueous dispersion and enhanced luminescence efficiency of the core-NPs make them an ideal luminescent material for luminescence bioimaging and optical biosensors.     

Re-exchange of Fe and Cu at the interface in sintered Nd–Fe–B magnets: A method to eliminate Fe precipitation at grain boundaries

According to the decoupling hypothesis for magnetic grains, the coercivity in sintered Nd–Fe–B magnets is increased after Cu doping, which is due to the formation of non-magnetic grain boundaries. However, this method partially fails, and ferromagnetic Fe-segregation occurs at the grain boundary. We discovered both experimentally and through calculation that the Fe content at the grain boundaries can be tuned across a wide range by introducing another element of Ag. Segregated Fe at high temperature at the grain boundary re-dissolves into Nd₂Fe₁₄B grains during annealing at low temperature. Both configurable and magnetic entropies contribute a large driving force for the formation of nonmagnetic grain boundaries. Almost zero Fe content could be achieved at the grain boundaries of sintered Nd–Fe–B magnet.     

纳米晶永磁Pr2Fe14B微磁学有限元法的模拟计算研究

根据实验数据，构造了接近实际纳米晶永磁Pr2Fe14B的样品，用微磁学有限元法进行了模拟计算.计算结果表明，晶界处各向异性的下降会导致矫顽力减小、剩磁值增大，而晶界处交换作用常数的减小则会使剩磁值减小、矫顽力增大.通过对实验样品的模拟研究发现，晶界处各向异性和交换作用常数的共同减小能够同时拟合出真实的矫顽力和剩磁值.模拟计算与实验在退磁曲线形状上的差距则说明模拟还存在不足. 关键词： 纳米晶永磁 磁滞回线 矫顽力 剩磁     

Ce3+离子激活的(氟)磷酸盐基质发光材料的光谱特性

利用高温固相反应方法合成了Ce3+离子激活的氟磷酸盐基质发光材料NNa2Gd0.99Ce0.001PO4F2和多磷酸盐基质发光材料MGd0.99Ce0.01(P03)4(M=Na,K,Cs).通过光谱研究发现,在Na:Gd0 99ce-tP0.F:的真空紫外-紫外(VUV-UV)激发光谱上,可以看到Ce3+离子中心波长...     

固体材料中稀土离子荧光寿命的研究

本文用激光激发和荧光探测技术测定了Eu2+、Eu3+、Ce3+、Dy3+、Nd3+和Tb3+离子在一些发光材料和激光晶体等固体中的荧光寿命,其寿命值从几十纳秒到几毫秒.为此对寿命测量技术进行了探讨以适应如此宽广的时间范围.从测得的寿命数据解释了材料内激活离子的性质和相互作用.