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.     

Grain boundary interdiffusion in the case of concentration-dependent grain boundary diffusion coefficient

The grain boundary diffusion in a binary system which exhibits a grain boundary phase transition is considered in the framework of Fisher's model. The kinetic law of the growth of the grain boundary phase and the distribution of the diffusant near the grain boundary are calculated. The method of determining of the concentration dependence of the grain boundary diffusion coefficient from the experimentally measured penetration profiles of the diffusant along the grain boundaries is suggested. The experimental results on Zn diffusion in Fe(Si) bicrystals, Ni diffusion in Cu bicrystals and grain boundary grooving in Al in the presence of liquid In are discussed in light of the suggested model.     

烧结Nd-Fe-B磁体的微观结构和冲击韧性研究

对烧结Nd₁₅Fe_72-xCo_yNb_xB₈(y=0, 5;x=0, 05, 10, 15, 20, 25)永磁体的微观结构和冲击韧性及二者间的关系进行了研究.结果表明,添加Nb能够改善Nd-Fe-B磁体的微观结构,提高磁体的冲击韧性.当无Co磁体中Nb的原子百分含量为15%时,其冲击韧性达到最大;对于添加了Co的磁体,其冲击韧性的关键词：Nd-Fe-B冲击韧性微观结构晶界     

Effect of Grain Boundary Segregation and Migration on Diffusion Profiles: Analysis and Experiments

In many experimental studies, curved penetration profiles are observed for grain boundary diffusion performed in the B kinetics regime in contrast to the shape expected from the solutions of the second Fick's equation. To explain these curvatures the effects of grain boundary structure, grain boundary migration, and grain boundary segregation have been successively proposed in the literature. Using previous data for Cu–Ag and Cu–Ni and new ones on Cu–Fe and Cu–Zn systems we will show how it is possible to separate all these possible contributions and how, knowing the true origin of the curvature, one can deduce much quantitative information impossible (or very difficult) to obtain by other techniques.     

Grain Boundary Motion during Ag and Cu Grain Boundary Diffusion in Cu Polycrystals

Grain boundary (GB) motion in high-purity Cu material (5N8 and 5N Cu) is investigated using the results of radiotracer GB diffusion measurements with tracers exhibiting fundamental differences in the solute-matrix atom interactions. The results on GB solute diffusion of Ag (revealing a miscibility gap in the Ag-Cu phase diagram) and Au (forming intermetallic compounds with Cu) in Cu and on Cu self-diffusion are analyzed.The initial parts of the Ag and Cu penetration profiles turned out to be substantially curved. The profile curvature is explained via the effect of GB motion during ^110m Ag and ⁶⁴Cu GB penetration. The activation enthalpies of GB motion in these two independent measurements occurred to be very close, 95 and 103 kJ/mol, respectively. Moreover, these values turn out to be close, but still somewhat larger than the activation enthalpy of Cu GB self-diffusion in Cu material of the same very high purity, Q ^Cu _gb = 72 kJ/mol. Although tracer diffusion measurements of Au GB diffusion in Cu yielded only limited information on GB motion, the absolute values of GB velocities are consistent with those calculated from the Ag and Cu GB diffusion data.     

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.     

The Effect of Pressure on Indium Diffusion along 〈001〉 Tilt Grain Boundaries in Copper Bicrystals

The effect of pressure on the diffusion of indium along two grain boundaries (GBs) in copper bicrystals has been investigated. The GBs studied were of symmetrical tilt type with a 001 misorientation axis. The tilt angle of one GB was 36.5°, which corresponds to the near 5 coincidence orientation, where is the inverse density of the coincidence sites in the two misoriented crystal lattices. The other GB was a general boundary with a tilt angle of 45°. The diffusion along the 001 tilt axis has taken place at the temperature of 923 K and under argon gas pressures up to 1 GPa. The following activation volumes have been found: 0.94±0.11 _Cu for bulk diffusion,–0.5 ±0.7 _Cu for the diffusivity of the near 5 GB and –0.6±0.3 _Cu for the diffusivity of the 45° 100 GB, where _Cu is the atomic volume of copper. Two interpretations of this result seem plausible. The first interpretation is that the In atoms diffuse along the 001 tilt axis by an instertitialcy mechanism. It is known that for such a diffusion mechanism the activation volume is close to zero. The alternative explanation bases on the observation that the parameter measured is the GB diffusivity, which depends on the product of the GB diffusion coefficient and the segregation factor. An enhancement of the In segregation under pressure would lead to an increase of the GB diffusivity. It seems plausible that both interpretations are true and the fact that the atomic volume of In is a factor of 2.2 larger than that of Cu plays an important role both for the increased segregation of In under pressure and the diffusion mechanism.     

Theory of grain boundary motion during high-temperature DIGM

A theory of diffusion induced grain boundary migration (DIGM) is presented for high temperatures where volume diffusion of solute atoms out of the grain boundary is important. It is shown that due to the presence of a gradient term in the expression for the free energy of solid solution, even a relatively small discontinuity in the solute distribution across the gain boundary provides enough driving force for grain boundary migration. From the expression obtained for the grain boundary velocity the coefficient for the Ni diffusion across the grain boundaries in a Cu(Ni) polycrystal has been estimated.     

Microstructure Observations for Diffusion Induced Recrystallization and Diffusion Induced Grain Boundary Migration on Surfaces of Zincified Cu Bicrystals With [1 1 0] Twist Boundaries

The formation behavior of the fine-grain region alloyed with Zn due to diffusion induced recrystallization (DIR) in the Cu(Zn) system was experimentally examined for the surfaces polished in different manners using a Cu bicrystal containing a [1 1 0] twist boundary with a misorientation angle of = 46° zincified at 673 K for 2.88 × 10⁴ s with Cu-15 wt% Zn and Cu-30 wt% Zn alloys by a capsule zincification technique. The extent and morphology of the fine-grain DIR region vary depending on the surface conditions and the composition of the Zn-source Cu-Zn alloy. For the specimen with the surface electrolytically polished in an etchant consisting of 20 vol% of nitric acid and 80 vol% of methanol, no DIR region was formed on the whole surface when the Cu-15 wt% Zn alloy was used as a Zn source.In order to observe the morphology of the moving grain boundary owing to diffusion induced grain boundary migration (DIGM) without influences of DIR, Cu bicrystals with [1 1 0] twist boundaries of = 32 ( 27), 39 ( 9), 46, 51 ( 11) and 55° were electrolytically polished in the etchant mentioned above. The polished Cu bicrystals were zincified at 673 K for 2.88 × 10⁴ s using the Cu-15 wt% Zn alloy as a Zn source. Remarkable surface relief and clear slip bands were recognized on the surfaces due to DIGM for the specimens with the 32 ( 27) and 46° boundaries. The moving boundary became zigzag owing to the slip bands parallel to the moving direction. On the other hand, such surface relief and slip bands were not observed for the specimens with the 39 ( 9), 51 ( 11) and 55° boundaries. The moving boundary was considerably irregular for = 39° whereas rather smooth for = 51 ( 11) and 55°. The migration behavior of the grain boundary was not affected by the interruption of the zincification.     

Diffusion along the Grain Boundaries in Crystals with Dislocations

A generalization of the Fisher model of the grain boundary diffusion is suggested, which takes into account the diffusion along short circuit diffusion paths (i.e., dislocations) in the bulk of crystalline grains. For the B-regime of the grain boundary diffusion, three different penetration modes have been found: at the short times the penetration depth of the element diffusing along the grain boundary is given by the Whipple solution of the Fisher model, but with the pipe diffusion coefficients along the dislocation cores instead of the volume diffusivities; at the intermediate times the penetration depth is a weak function of time, and at the large times the penetration depth again increases with time according to the Whipple solution, however, the rate of this increase is much smaller than in the initial period of time. The applications of the model for diffusion in nanomaterials are discussed.     

Diffusion Along Migrating Grain Boundaries

The paper summarizes recent experiments on diffusion at migrating grain boundaries (GBs) occurring during discontinuous reactions, like discontinuous precipitation (DP) and diffusion induced grain boundary migration. Analytical electron microscopy was used for measurements of the solute concentration across individual solute-depleted lamellae. These data combined with information on the growth velocity and the thickness of an individual lamella allowed the determination of the local values of the diffusivities of the moving reaction front of the DP cell in Al–Zn, Ni–Sn, Cu–In and Co–Al alloys. The obtained diffusivities and activation energies are very similar to the relevant parameters of stationary GBs. This allows us to conclude that there is no significant difference in the rates of diffusion along migrating and stationary GBs in the systems investigated. It is therefore believed that the diffusivity values of the moving reaction front of the DP reaction can be a source of reliable information on interfacial diffusion characteristics, especially in systems and/or at temperatures where radiotracer data are not readily available.     

烧结Nd-Fe-B磁体的磁性能一致性与其微观结构的关系

分析了微观结构和热处理工艺对矫顽力的影响,发现在矫顽力一定的情况下,磁体的微观结构越“差”,则保证不同批次磁体矫顽力变化不大于某一给定值所需的工艺条件就越严格;反之则越宽松.就同一炉产品而言,微观结构越好的磁体,其矫顽力受烧结(热处理)炉温度梯度的影响越小,其结果是该炉产品的一致性越高.反之,受温度梯度的影响越大,磁体的一致性也就越低.该研究结果说明:在条件许可的情况下,应首先考虑通过改善磁体的微观结构来提高磁性能一致性.关键词：Nd-Fe-B永磁体微观结构内禀矫顽力一致性     

Effect of High-Temperature Structure and Diffusion on Grain-Boundary Diffusion Creep in fcc Metals

Molecular dynamics simulations of high-energy twist and tilt bicrystals of fcc palladium reveal a universal, liquid-like, isotropic high-temperature diffusion mechanism, characterized by a rather low self-diffusion activation energy that is independent of the boundary type or misorientation. Medium-energy grain boundaries exhibit the same behavior at the highest temperatures; however, at lower temperatures the diffusion mechanism becomes anisotropic, with a higher, misorientation-dependent activation energy. Our simulations demonstrate that the lower activation energy at elevated temperatures is caused by a structural transition, from a solid boundary structure at low temperatures to a liquid-like structure at high temperatures. We demonstrate that the existence of such a transition has important consequences for diffusion creep in nanocrystalline fcc metals. In particular, our simulations reveal that in the absence of grain growth, nanocrystalline microstructures containing only high-energy grain boundaries exhibit steady-state diffusion creep with a creep rate that agrees quantitatively with that given by the Coble-creep formula. Remarkably, the activation energy for the high-temperature creep rate is the same as that characterizing the universal high-temperature diffusion in high-energy energy bicrystalline grain boundaries.     

The stability of triple junctions during the grain boundary diffusion process

The grain boundary diffusion in a system with triple junctions is considered in such a geometry, in which the flows of diffusing atoms meet at the triple line. The solutions of the diffusion equation is given in the frameworks of Fisher's model and under the assumption of quasi-stationary distribution of the diffusing atoms along the grain boundaries. The change of the mechanical equilibrium at the triple junction due to the increase of the concentration of solute atoms is considered. It is shown that under some circumstances the triple junction looses its stability with respect to migration in the direction to the diffusion source. The stability diagrams in the segregation-diffusivity parameter space are plotted.     

Influence of interdiffusion on the electrical conductivity of multilayered metal films

The annealing-time dependence of the electrical conductivity of multilayered single-crystal and polycrystalline metal films has been analyzed theoretically within the frame of the semi-classical approach. It is demonstrated that changes in the electrical conductivity which are caused by the diffusion annealing allow for investigating the processes of the bulk and grain-boundary diffusion, and for estimating the coefficients of the diffusion. The electrical conductivity was calculated and the numerical analysis of the diffusion-annealing time dependence was performed at various parameters.     

Evolution of Pore Ensembles Located at the Grain Boundaries in Cu and Cu-5 at.% Sn

The kinetics of pore coalescence in ensembles located at the grain boundaries in Cu and Cu-5 at. % Sn has been studied by optical and scanning electron microscopy at 500 and 800°C. In the case of pure Cu the evolution of the pore ensemble followed the kinetical law ¯4 t, where ¯ is the average pore radius and t is the ageing time. This law is typical for a grain boundary diffusion controlled process. However, in the case of the Cu-5 at. % Sn alloy the kinetical law obeyed the ¯3 t relationship, which is characteristic for a reaction controlled process. The reaction in question is the generation of vacancies on the surfaces of the pores. The importance of the surface reaction controlled mass transfer process in alloys is discussed. The grain boundary self-diffusivity and the kinetical coefficients of the reaction are determined and analyzed.     

Co-Segregation Effects on Boundary Migration

We analyze the effect of co-segregation on the mobility of grain boundaries within the framework of the impurity drag theory originally proposed by Cahn and Lücke and Stüwe for an ideal solution. The new derivation extends this model to the case where there are two types of impurities (or three components in the alloy). Since the resultant expression for the boundary mobility is complicated, numerical solutions were obtained for several cases to show how co-segregation affects the boundary mobility. Depending on the relative diffusivities of the two impurities which are both attracted to the boundary, the mobility may either increase or decrease with increasing concentration of one of the impurities. When one of the impurities is attracted to the boundary and the other repelled from the boundary, increasing the concentration of the attractive impurity can lead to a sharp decrease in the boundary mobility.     

The Lattice Model for Addressing Phenomenological Diffusion Problems Associated with Grain Boundaries

Mapping a phenomenological diffusion problem onto a lattice permits lattice-based random walk theory to address the problem. The solution is generally carried out using Monte Carlo methods. This paper reviews the substantial progress that has been made with this method for tracer diffusion associated with grain boundaries.