利用Pr_(70)Cu_(30)晶界扩散改善烧结钕铁硼废料矫顽力的研究

钕铁硼磁体制备过程中出现的部分块体废料由于矫顽力较低,性能难以满足使用要求.本文主要通过晶界扩散技术来提高废料磁体的矫顽力.采用Pr_(70)Cu_(30)合金作为扩散介质,对烧结钕铁硼废料磁体进行了晶界扩散处理,研究了扩散温度、扩散时间和回火时间对扩散后的磁体性能的影响.结果显示,800℃下扩散3 h,磁体的矫顽力从原来的7.88 kOe(1 Oe=79.5775 A/m)提升至11.55 kOe,提升幅度为46.6%,同时剩磁没有明显降低.扩散后回火对矫顽力的提升有一定的作用.800℃下扩散4h后的磁体在500℃回火3h后,最高矫顽力可达11.97 kOe,比原磁体废料提高了51.9%,接近成品磁体的水平.显微组织分析证实了晶界扩散的作用.扩散处理后的磁体中,主相晶粒间形成了连续晶间相,起到有效的磁隔离作用,有利于矫顽力的提高.研究还发现,Pr_(70)Cu_(30)晶界扩散虽然可以使磁体腐蚀电位上升,但也会增加腐蚀电流密度,不利于磁体抗腐蚀性的改善.本文工作对于提高材料的成品率具有重要意义.     

Effects of terbium sulfide addition on magnetic properties,microstructure and thermal stability of sintered Nd-Fe--B magnets

To increase coercivity and thermal stability of sintered Nd–Fe–B magnets for high-temperature applications, a novel terbium sulfide powder is added into(Pr_(0.25)Nd_(0.75))_(30.6)Cu_(0.15)Fe_(bal)B_1(wt.%) basic magnets. The effects of the addition of terbium sulfide on magnetic properties, microstructure, and thermal stability of sintered Nd–Fe–B magnets are investigated.The experimental results show that by adding 3 wt.% Tb_2S_3, the coercivity of the magnet is remarkably increased by about 54% without a considerable reduction in remanence and maximum energy product. By means of the electron probe microanalyzer(EPMA) technology, it is observed that Tb is mainly present in the outer region of 2:14:1 matrix grains and forms a well-developed Tb-shell phase, resulting in enhancement of HA, which accounts for the coercivity enhancement.Moreover, compared with Tb_2S_3-free magnets, the reversible temperature coefficients of remanence(α) and coercivity(β) and the irreversible flux loss of magnetic flow(hirr) values of Tb_2S_3-added magnets are improved, indicating that the thermal stability of the magnets is also effectively improved.     

Magnetic and structural investigations on substituted Pr2Co17-xTx systems (T= Fe, Mn, Cr, Cu and Al)

Magnetic and structural characteristics of Pr₂Co₁₇-based ternaries, in which Co is partly replaced by other transition elements, namely Fe, Mn, Cr, Cu and Al, have been investigated. The objective of the work was to explore the possibility of enhancing the anisotropy of Pr₂Co₁₇ to the point that it would be useful for permanent magnet fabrication. X-ray diffraction indicates that all the systems studied occur in the rhombohedral Th₂Zn₁₇ structure. The cell constants increase as Fe, Mn, etc., are introduced in the system, which indicates that substitution occurs in the Co sublattice. The Curie temperatures, T_c, decrease monotonically with increasing x in the order Fe < Cu < Mn < Al < Cr. The saturation magnetization, M_s, increases with increasing x for the Fe system with x 8. For x #62; 8 in the Pr₂Co_17-xFe_x system and in all other ternary systems st died, M_s decreases with x, the magnitude of the effect being in the order Cr #62; Al #62; Mn #62; Cu. The rate of decrease is larger than that expected as a simple dilution except for the systems containing Cu. Significant modification of the anisotropy characteristics of Pr₂Co₁₇ is observed upon substitution. The planar anisotropy of Pr₂Co₁₇ becomes uniaxial with Fe (x 4) and Mn (x 2) substitutions. With Cr and Al substitutions, the plane-seeking tendency of Pr₂Co₁₇ is significantly weakened.     

Production of thick high-performance sintered neodymium magnets by grain boundary diffusion treatment with dysprosium–nickel–aluminum alloy

A novel grain boundary diffusion (GBD) treatment with a Dy–Ni–Al eutectic alloy powder allowed Dy to penetrate into sintered plates of Nd–Fe–B magnet as thick as 5 mm. The coercivity of the magnet was increased from a value of 1160 kA/m (14.5 kOe) to 1760 kA/m (22 kOe). This was achieved without any marked decrease in remanance and with a high squareness.     

Magnetic behavior of Pr1 − xMxCo5 compounds (M = Ti, Zr and Hf)

Magnetic characteristics of Ti-, Zr- and Hf-substituted PrCo₅ alloys have been studied over the temperature range from 77 to 300 K and for applied fields up to 20 kOe. It is established that Ti, Zr and Hf substitute for Pr. Single-phase materials are formed for all values of x up to 0.2 in the system Pr_1−xZr_xCo₅ but for x only up to 0.1 for Pr_1−xTi_x Co₅ and Pr_1−xHfxCo₅ alloys. Larger amounts of Zr can be substituted if the material is made hyperstoichiometric in Co, e.g., Pr_0.7Zr_0.3Co_5.5. All the alloys show a decrease in magnetic moment and an increase in Curie temperature as x increases. Anisotropy fields decrease as x increases at 295 K. Anomalous behavior is observed at 77 K, suggested that these ternary alloys may have a cone structure at this temperature.     

Influence of misch metal content on microstructure and magnetic properties of R–Fe–B magnets sintered by dual alloy method

MM_(14)Fe_(79.9)B_(6.1)/Nd_(13.5)Fe_(80.5)B_6 magnets were fabricated by dual alloy method(MM, misch metal). Some magnets have two Curie temperatures. Curie temperatures T_(c1)corresponds to the main phase which contains more La Ce, and T_(c1) decreases from 276.5?C to 256.6?C with the content of MM increasing from 30.3 at.% to 50.6 at.%. The variation of Br with the increase of MM indicates the existence of inter-grain exchange coupling in the magnets. When MM/R ≤ 30.3 at.%,the magnetic properties can reach the level of the intrinsic coercivity Hcj≥ 7.11 kOe and the maximum energy product(BH)max≥ 41 MGOe. Compared with Nd, La and Ce are easier to diffuse to the grain boundaries in the sintering process,and this will cause the decrease of H_(cj) Due to the diffusion between the grains, the atomic ratio of La, Ce, Pr, and Nd in each grain is different and the percentage of Nd in all grains is higher than that in misch metal.     

Magnetic hysteresis in rapidly quenched rare-earth alloys

The magnetic and structural properties of rapidly quenched (Pr₈₀Ga₂₀)_100-xFe_x, RTbFe and RTbFe(Co)M alloys are examined over a wide range of chemical compositions, where R ≡ Pr, Sm, MM and M ≡ B and Si. The Ga-containing samples show relatively high coercive fields (up to 3 kOe) in the amorphous state which subsequently disappear after crystallization. On the other hand, the high coercive fields (≈5 kOe) of melt-spun RTbFe samples decrease slightly after crystallization but their magnetic moment increases substantially. Melt-spun RTbFe(Co)M samples are generally magnetically soft in the as-quenched state. Magnetic hardening is produced by annealing the samples around 750°C leading to coercive fields which could not be measured with an ordinary electromagnet (H_c #62; 23 kOe). The best properties have been obtained on a Pr₁₄Fe₇₁B₁₅ sample with a coercive field of 8 kOe and an energy product of 8.5 MGOe. Thermomagnetic data show that a structural transformation takes place upon heating the samples to 750°C. The Curie temperature of the precipitate phase is around 320°C while that of the as-quenched phase is around 160°C. Transmission electron microscope studies show a very fine precipitate structure with a precipitate size below 100 Å. The precipitate phase is believed to be highly anisotropic leading to the observed hard magnetic properties.     

Simultaneous enhancement in coercivity and remanence of Nd2Fe14B permanent magnet by grain boundary diffusion process using NdHx

We have successfully developed a Dy-free grain boundary diffusion process with neodymium hydride (NdH_x) alloy to the permanent magnet Nd₂Fe₁₄B powders using hydrogenation – disproportionation – desorption – recombination (HDDR) method. All the diffusion treatments were performed at 700–800 °C for various annealing time under the high vacuum with rotating diffusion method that effectively control the abnormal grain growth. The coercivities of Dy-treated Nd₂Fe₁₄B powders were varied from 9.5 kOe to 13.2 kOe but the remanence was decreased to 8.1 kG (10% reduction) depending on dysprosium hydride (DyH_x) content and diffusion treated time. However, the coercivity and remanence of Dy-free diffusion treated powder have been increased to 12.2 kOe (28.5% enhancement) and 11.1 kG (22% enhancement) at the optimal diffusion treatment (800 °C for 3 h), respectively. This unique simultaneous enhancement is to isolate the magnetic coupling between Nd₂Fe₁₄B grains by creating non-magnetic Nd grain boundaries and enhance the alignment of the Nd₂Fe₁4B hard magnetic phase, fabricated by optimal diffusion conditions.     

Effects of post-sinter annealing on microstructure and magnetic properties of Nd–Fe–B sintered magnets with Nd–Ga intergranular addition

We investigate the effects of post-sinter annealing on the microstructure and magnetic properties in B-lean Nd–Fe–B sintered magnets with different quantities of Nd–Ga intergranular additions. The magnet with fewer Nd–Ga additions can enhance 0.2 T in coercivity, with its remanences nearly unchanged after annealing. With the further increase of the Nd–Ga addition, the annealing process leads coercivity to increase 0.4 T, accompanied by a slight decrease of remanence. With the Nd–Ga addition further increasing and after annealing, however, the increase of coercivity is basically constant and the change of remanence is reduced. Microstructure observation indicates that the matrix grains are covered by continuous thin grain boundary phase in the magnets with an appropriate Nd–Ga concentration after the annealing process. However, the exceeding Nd–Ga addition brings out notable segregation of grain boundary phase, and prior formation of part RE6 Fe13 Ga phase in the sintered magnet. This prior formation results in a weaker change of remanence after the annealing process.Therefore, the diverse changes of magnetic properties with different Nd–Ga concentrations are based on the respective evolution of grain boundary after the annealing process.     

Interactions between vacancies and prismatic Σ3 grain boundary in α-Al_2O_3:First principles study

Interactions between vacancies and Σ3 prismatic screw-rotation grain boundary in α-Al_2O_3 are investigated by the first principles projector-augmented wave method.It turns out that the vacancy formation energy decreases with reducing the distance between vacancy and grain boundary(GB) plane and reaches the minimum on the GB plane(at the atomic layer next to the GB) for an O(Al) vacancy.The O vacancy located on the GB plane can attract other vacancies nearby to form an O–O di-vacancy while the Al vacancy cannot.Moreover,the O–O di-vacancy can further attract other O vacancies to form a zigzag O vacancy chain on the GB plane,which may have an influence on the diffusion behavior of small atoms such as H and He along the GB plane of α-Al_2O_3.     

Effect of Hg addition on synthesis of Bi-based superconductors

We have investigated the effect of Hg addition on the superconducting properties of BiSrCaCuO system. Polycrystalline samples with nominal composition Bi₂Sr_2−xHg_xCa₁Cu₂O_y and Bi₂Sr_2−xHg_xCa₂Cu₃O_y (x=0.3) were synthesized and used to investigate the phase evolution by XRD, superconducting behaviour by R–T measurement and the structural grain boundary effects by SEM. From these measurements, it has been noticed that the phases obtained with both types of compositions are the same as Bi2212 but the T_c values are different. With additional annealing, T_{c zero} values were raised from 60 to 72 K in Bi₂Sr_2−xHg_xCa₁Cu₂O_y and 64 to 92 K in Bi₂Sr_2−xHg_xCa₂Cu₃O_y. Also, an improved grain boundary linkage has been observed by SEM for the 92 K sample.     

A comparison of FePt thin films with HfO2 or MnO additive

The influence of oxide additives on the magnetic and structural properties of FePt L1₀ thin films has been studied. FePt films with HfO₂ additive grown on a 5 nm MgO buffer showed a primarily random texture for both as-deposited and annealed samples. The average grain size was limited to 10 nm and the perpendicular coercivity was 1.3 kOe for a 10 nm thick FePt +20% HfO₂ film annealed at 650°C for 10 min. In direct contrast, MnO additive neither limited grain size nor L1₀ ordering in annealed FePt films. A 10 nm thick FePt+20% MnO film grown on a 5 nm MgO buffer showed a unique discontinuous microstructure composed of clusters of (0 0 1) textured L1₀ grains after being annealed at 650°C for 10 min. The average size of the grains making up these clusters was 50 nm and the perpendicular coercivity of the film exceeded 7 kOe.     

三元Co_(79)Zr_(18)Cr_3合金中高矫顽力

通过在Co_(82)Zr_(18)合金中添加过渡族元素Cr的方法,利用快淬工艺,制备出了Co_(82-x)Zr_(18)Cr_x(x=0,2,3,4)快淬合金薄带,利用磁性测量、X光衍射、热磁分析、扫描电子显微镜,对其磁性能、相组成、微结构进行了研究,实验结果表明,在Co_(82)Zr_(18)合金中添加少量的Cr可以使其矫顽力(iHc)显著提高,其中,Co_(79)Zr_(18)Cr_3快淬薄带经600℃退火处理后iHc=6.5 kOe.相分析发现,600℃退火后的Co_(79)Zr_(18)Cr_3快淬薄带由单一Co_(11)Zr_2相组成,Cr原子进入到了Co_(11)Zr_2相的晶格之中替换了原子半径相对较小的Co原子,这导致了Co_(11)Zr_2居里温度(T_C)的降低却使其磁晶各向异性场(Ha)显著提高;另一方面,通过微结构研究发现,未退火的Co_(79)Zr_(18)Cr_3快淬薄带由50—80 nm的等轴晶粒组成,经600℃退火后,其晶粒形态并未发生改变然而晶粒尺寸却增长到400—500nm。     

Nanocrystalline Pr0.5Sm0.5Co5 alloy obtained by mechanical milling

Starting from arc-melted alloys, nanostructured Pr_0.5Sm_0.5Co₅ powders were synthesized by mechanical milling and subsequent vacuum annealing during short times to develop an optimal microstructure with high hard magnetic properties. The best magnetic properties were obtained for the stoichiometric Pr_0.5Sm_0.5Co₅ powders milled for 4 h and annealed at 800 °C for 1 min with a high coercitivity of 13.5 kOe, a high M_r/M_max ratio of 0.72 and a maximum energy product of 11 MGOe. From X-ray diffraction and transmission electron microscopy, CaCu₅-type phase and an average grain size of about 12 nm were determined in the annealed powders, and we calculated that 59% of the volume of the grains/crystallites are exchange-coupled. The observed magnetic hardening is associated to the high magnetic anisotropy field of the PrCo₅ and SmCo₅ phases and also to the microstructure developed by the processing used.     

Critical current density behaviors across a grain boundary inclined to current with different angles in YBa_2Cu_3O_(7-δ) bicrystal junctions

The critical current density behaviors across a bicrystal grain boundary(GB) inclined to the current direction with different angles in YBa_2Cu_3O_(7-δ) bicrystal junctions in magnetic fields are investigated.There are two main reasons for the difference in critical current density in junctions at different GB inclined angles in the same magnetic field:(i) the GB plane area determines the current carrying cross section;(ii) the vortex motion dynamics at the GB affects the critical current value when the vortex starts to move along the GB by Lorentz force.Furthermore,the vortex motion in a bicrystal GB is studied by investigating transverse(Hall) and longitudinal current–voltage characteristics(I–V_(xx) and I–V_(xy)).It is found that the I–V_(xx) curve diverges from linearity at a high driving current,while the I–V_(xy) curve keeps nearly linear,which indicates the vortices inside the GB break out of the GB by Lorentz force.     

Magnetic properties of Sm–Co–B-based nanocomposite magnets

The magnetic properties of nanocomposite melt-spun magnets with composition Sm_16−xCo_68+xB₁₆ (x=0–10, 2 at% interval) and Sm₈Co_92−yB_y (y=10–18, 2 at% interval) have been studied systematically. Several ribbons were fabricated with a wheel speed of 50 m/s, followed by annealing in the temperature range of 700–800°C for 2.5–40 min. XRD results and magnetization versus temperature curves showed that almost all of the samples were composed of the tetragonal Sm₂Co₁₄B and rhombohedral SmCo₁₂B₆ phases which are not magnetically hard at room temperature. However, a relatively high coercivity in the range of 3.5–5.5 kOe has been obtained in these samples. The highest coercivity of 5.5 kOe and a very promising β value of −0.28%/°C were obtained in Sm₈Co₇₄B₁₈ ribbons annealed at 750°C for 5 min. The high coercivities are attributed to the small grain size of the 2 : 14 : 1 phase, in which the large surface areas enhance its effective anisotropy, and make it uniaxial type.     

Crystal structure of YBa2Cu3O7−x thin films prepared by pulsed laser deposition with substrate bias voltage

The crystal structure of YBa₂Cu₃O_7−x thin films has been investigated by cross-section transmission electron microscopy. The samples were deposited on MgO (100) substrates at 670°C with substrate bias voltages of ±300 V. For the unbiased case, c-axis, a-axis and (103) oriented domains normal to the substrate surface were observed. In this film, the c-axis oriented domains are dominant, but the crystal often exhibits a longer c-lattice constant than that of the YBa₂Cu₃O_7−x system, so extra cationic layers are inserted in the YBa₂Cu₃O_7−x intrinsic stacking sequence. For the case of −300 V, rotated domains were dominant in the entire film; however, c-axis oriented domains also grow from the substrate surface. Small-angle semicoherent grain boundaries between them were observed. In the case of +300 V, all the grains show c-axis oriented YBa₂Cu₃O_7−x. The degree of preferential orientation of the grains is reduced at negative bias voltage of −300 V and the structure defects are reduced by applying a positive bias of +300 V.     

Improvement in coercivity,thermal stability,and corrosion resistance of sintered Nd-Fe-B magnets with Dy_(80)Ga_(20) intergranular addition

To investigate the coercivity,corrosion resistance,and thermal stability of Nd-Fe-B magnets,their properties were investigated at room and high temperature before and after doping with Dy_(80)Ga_(20)(at.%) powder.The coercivity of the magnets increased from the undoped value of 12.72 kOe to a doped value of 21.44 kOe.A micro-structural analysis indicates that a well-developed core-shell structure forms in the magnets doped with Dy_(80)Ga_(20) powder.The improvement in magnetic properties is believed to be related to the refined and uniform matrix grains,continuous grain boundaries,and a hardened(Nd,Dy)_2Fe_(14)B shell surrounding the matrix grains.Additionally,the doped magnets exhibit an obvious improvement in thermal stability.For the magnets with added Dy_(80)Ga_(20) powder,the temperature coefficients of remanence(α) and coercivity(β) increased to-0.106%℃~(-1) and-0.60%℃~(-1) over the range 20-100 ℃,compared to temperature coefficients of-0.117%℃~(-1)(α) and-0.74%℃~(-1)(β) in the regular magnets without Dy_(80)Ga_(20) powder.The irreversible loss of magnetic flux(Hirr) was investigated at different temperatures.After being exposed to 150 ℃ for 2 h,the Hirr of magnets with 4 wt.%Dy_(80)Ga_(20) decreased by ~95%compared to that of the undoped magnets.The enhanced temperature coefficients and Hirr indicate improved thermal stability in the doped Nd-Fe-B magnets.The intergranular addition of Dy_(80)Ga_(20) also improved the corrosion resistance of the magnets because of the enhanced intergranular phase.In a corrosive atmosphere for 96 h,the mass loss of the sintered magnets with 4 wt.%Dy_(80)Ga_(20) was 2.68 mg/cm~2,less than 10%of that suffered by the undoped magnets(28.1 mg/cm~2).     

Barrier or easy-flow channel: The role of grain boundary acting on vortex motion in type-Ⅱ superconductors

Grain boundaries(GBs),as extremely anisotropic pinning defects,have a strong impact on vortex motion in type-Ⅱsuperconductors,and further on the macro level dominates the superconductivity for example the critical current density.Many previous studies indicated that mostly GB plays the role of a strong barrier for vortex motion,while an easy-flow channel just under some certain conditions.In order to thoroughly make clear of the questions of what is exactly the role of GB on vortex motion and how it works,in this article we developed a large scale molecular dynamic model and revealed the action of GB on vortex motion in type-Ⅱ superconductors.The most significant finding is that the role of GB on vortex motion can be changeable from a barrier to an easy-flow channel,and which is intrinsically determined by the competition effect correlated with its action on vortex between in the GB and no-GB regions.Such the competition effect essentially depends on the attributes of both the GB(described by the GB strength and angle θ) and no-GB pining regions(by the relative disorder strength α_p/a_v).Specifically,for a YBa_2 Cu_3 O_(7-x)(YBCO) sample,to obtain a clear knowledge of vortex motion in GB region,we visualized the three typical trajectories of vortices during the three vortex movement stages.Further,in order to understand how GB results in the macro current-carrying property,corresponding to the current-voltage relation of the YBCO conductor,we obtained the average velocity v_y of vortices varying with their driving force,which is nearly identical with the previous observations.     

Phase equilibria at low oxygen partial pressure in the Y---Ba---Cu---O system

The phase equilibria around YBa₂Cu₃O_7−x (123) and YBa₂Cu₄O₈ (124) phases at low oxygen partial pressure (1 atm) were investigated by X-ray diffraction and thermal analysis. The coexistence of 123 and 124 phase was confirmed under 1 atm oxygen pressure. By using the high temperature X-ray diffraction method, the univariant reaction YBa₂Cu₃O_7−x+Cu₂OY₂BaCu₂O₂+O₂ was identified. The oxygen partial pressure dependence of several univariant reactions has been investigated and the existence of two invariant reactions of L+O₂YBa₂Cu₃O_7−x+ BaCuO₂+CuO+Cu₂O and L+Y₂BaCuO₅+O₂YBa₂Cu₃O_7−x+CuO+Cu₂O was deduced to occur at 1103 K under 0.0032 atm O₂ and at 1143 K under 0.0085 atm O₂, respectively.