The discovery of nanocrystalline Fe-based soft magnetic materials is less than ten years old. The first class of such materials was the melt-spun Fe-Si-B alloys containing small amounts of Nb and Cu (Yoshizawa et al. 1988). The Fe-Si-B-Nb-Cu amorphous phase transforms to a body-centered cubic (bcc) Fe-Si solid solution with grain sizes of about 10 nm during annealing at temperatures above the crystallization temperature. The presence of small amounts of Cu helps increase the nucleation rate of the bcc phase while Nb retards the grain growth. These "Finemet" alloys provide low core losses (even lower than amorphous soft magnetic alloys such as Co-Fe-Si-B), exhibit saturation induction of about 1.2 T, and exhibit very good properties at high frequencies, comparable to the best Co-based amorphous alloys. These were first developed in Japan and have stimulated a large amount of research and development worldwide to optimize the magnetic properties. There has been relatively little work in the United States in this area, however.
While many of the soft magnetic properties of Finemet-type nanocrystalline alloys are superior, they exhibit lower saturation inductions than Fe-metalloid amorphous alloys, mainly because of the lower Fe content to attain amorphization and because of the addition of Nb and Cu (or other elements to control the nucleation and growth kinetics). In order to remedy this problem, another class of Fe-based nanocrystalline alloys was developed by Inoue and coworkers at Tohoku University (Makino et al. 1997), which is commercialized by Alps Electric Co., Ltd., of Nagaoka, Japan (see also the Tohoku University site report, Appendix D). These "Nanoperm" alloys are based on the Fe-Zr-B system; they contain larger concentrations of Fe (83-89 at.%) compared to the Finemet alloys (~ 74 at.% Fe) and have higher values of saturation induction (~ 1.6-1.7 T). The Nanoperm nc alloys have very low energy losses at power frequencies (60 Hz), making them potentially interesting for electrical power distribution transformers. The issues of composition modification, processing, and the brittle mechanical behavior of these nanocrystalline/amorphous alloys are discussed by V.R. Ramanan in the first volume of this WTEC study, the proceedings of the May 8-9, 1997 panel workshop on the status of nanostructure science and technology in the United States (Ramanan 1998, 113-116). Figure 6.3 compares the soft magnetic properties of Finemet, Nanoperm, and other materials.
While there has been extensive research on these alloys, particularly in Japan and Europe, most of the development has been carried out in Japan. The Finemet family of alloys is marketed by Hitachi Special Metals. Vacuumschmelze GmbH (Germany) and Impky (France) also market similar alloys. The Nanoperm alloys are being commercialized by Alps Electric Co. (Japan). No extensive research nor any commercialization of these materials has been carried out in the United States.
The small single-domain nanocrystalline Fe particles in the amorphous matrix gives these alloys their unique magnetic behavior, the most dramatic being the lowest energy losses (narrowest B/H hysteresis loop) of any known materials, along with very high permeabilities. These alloys can also exhibit nearly or exactly zero magnetostriction. To date, these materials have been made by crystallization of rapidly solidified amorphous ribbons. Other methods that might provide geometrically desirable products should be explored or developed. Electrodeposition is one such method that requires further work. Electrodeposited nc Fe-Ni soft magnetic alloys are being developed in Canada.
The brittle nature of these materials is a problem for scaleup and transformer manufacture. The brittleness problem must be solved by finding less brittle materials or applying the handling and processing knowledge that exists for embrittled (after annealing) metallic glasses.
The first attempts to produce nanoscale microstructures to enhance the magnetic properties of the Nb-Fe-B permanent magnetic materials used mechanical alloying of blended elemental powders followed by heat treatment (Schultz et al. 1987). Since the grain structure so obtained does not exhibit any crystallographic texture-and limits the energy product-special processing methods such as die-upsetting were used by Schultz and coworkers (1989) to provide the crystallographic anisotropy. While the coercivities of these nanocrystalline alloys are high, the remanent magnetization is decreased.
Recent approaches to increasing the magnetic induction have utilized exchange coupling in magnetically hard and soft phases. The Fe-rich compositions (e.g., Fe90Nd7B3) result in a mixture of the hard Fe14Nd2B phase and soft a Fe phase. The nanoscale two-phase mixtures of a hard magnetic phase and a soft magnetic phase can exhibit values of remanent magnetization, Mr, significantly greater than the isotropic value of 0.5 Ms. This "remanence enhancement" is associated with exchange coupling between the hard and soft phases, which forces the magnetization vector of the soft phase to be rotated to that of the hard phase (Smith et al. 1996). Two important requirements for alloys to exhibit remanence enhancement are a nanocrystalline grain size and a degree of coherence across interphase boundaries sufficient to enable adjacent phases to be exchange-coupled. The significant feature of the exchange coupling is that it allows crystallographically isotropic materials to exhibit remanence values approaching those achieved after full alignment. Such two-phase nanoscale ferromagnetic alloys have been prepared by nonequilibrium methods such as melt-spinning, mechanical alloying, and sputter deposition. Besides the high reduced remanence, the material cost is reduced by reduction in the content of the expensive hard rare earth-containing magnetic phase.
The theoretical understanding of remanence enhancement appears to be developed to a degree enabling prediction of magnet performance; however, this performance, while a significant improvement over single-phase isotropic magnets, does not reach predicted values. Work is required on optimizing the orientation relationships between the hard and soft phases and the interphase properties (coherency) between them.
Research on nanocrystalline hard magnetic alloys has received attention worldwide. The U.S. efforts are summarized in the article by G.C. Hadjipanayis (1998, 107-112). While less research seems to be carried out in the world on these materials compared to the nanocrystalline soft magnetic alloys, some efforts exist in most countries. Notable programs are those of L. Schultz and coworkers at the Institut für Festköper und Werkstofforschung (IFW) in Dresden (see site report in Appendix B) and P.G. McCormick and coworkers at the University of Western Australia.
While the very low losses of the nc soft magnetic materials (Finemet or Nanoperm) are dependent on grain size for their properties, the hard magnetic nc alloys with remanence enhancement provide flexibility in processing, especially with powder materials. These remanence-enhanced nc hard magnetic alloys may find many applications as permanent magnet components.
The phenomenon of giant magnetoresistance (GMR)-the decrease of electrical resistance of materials when exposed to a magnetic field-was first reported in a number of multilayer ferromagnetic/nonferromagnetic thin film systems (Baibich et al. 1988). More recently, GMR was observed in equiaxed granular nanocrystalline materials (Berkowitz et al. 1992). In particular, GMR systems with low saturation fields offer a wide area for application in magnetoresistive devices. GMR sensors have a higher output than conventional anisotropic magnetoresistive sensors or Hall effect sensors. They can operate at higher magnetic fields than conventional magnetoresistive sensors. In multilayer systems the antiferromagnetic alignment of the ferromagnetic layers in zero field becomes ferromagnetic as the field is applied and causes a decrease in resistance. Granular materials that show GMR consist of small ferromagnetic single-domain particles with randomly oriented magnetic axes in a nonmagnetic matrix. An external field rotates the magnetic axes of all magnetic particles. The rotation towards complete alignment of all magnetic axes again reduces the resistance in a similar way as for multilayers. The GMR in granular systems is isotropic. The explanation for the GMR is spin-dependent scattering of the conduction electrons at the ferromagnetic/nonmagnetic interfaces and, to a lesser extent, within the magnetic grains. The GMR scales inversely with the average particle diameter.
There is worldwide research on the GMR effect. U.S. programs are reviewed by R. Shull and G.C. Hadjipanayis in the proceedings of the WTEC U.S. nanotechnologies workshop (Shull 1998, 43-58; Hadjipanayis 1998, 107-112). The NIST work described by Shull has provided material with the largest GMR values for the smallest switching fields. Japanese research on GMR includes studies in Prof. Fujimori's group at Tohoku University (see site report in Appendix D).
While the theory for GMR of spin-dependent scattering referred to above has been used as an explanation, other explanations taking into account interaction between magnetic regions have been proposed (El-Hilo et al. 1994). Combined theoretical and experimental studies should help to clarify the mechanism for this effect.
Other Ferromagnetic Nanocrystalline Materials
Magnetic nanocomposite refrigerants, which have four times the magnetocaloric effects of the best low temperature magnetic refrigerant, were developed by NIST and described by R. Shull (1998, 43-58). The entropy change at a given (low) temperature for a system of magnetic spins is enhanced when the isolated spins are clustered. Shull et al. (1993) have shown that the nanocomposite Gd3Ga5-xFexO12 gives superior magnetocaloric effects, which increase with x up to x = 2.5 and can be extended to higher temperatures than conventional materials.
Magnetostrictive materials such as Terfonol-D (Tb0.3Dy0.7Fe2) have been of scientific and technological interest in recent years. It is suggested by G.C. Hadjipanayis (1998, 107-112) that nanostructured magnetostrictive materials can have improved properties, such as lower saturation fields, with reduced anisotropy and in multilayers with alternate layers of magnetostrictive and soft magnetic materials that are exchange-coupled. Hadjipanayis states that most of the research in this area is carried out in Japan and Europe.
Nanocrystalline magnetic materials offer perhaps the nearest-term prospect of significant applications of bulk nanostructured materials. The remanence enhancement in two-phase hard/soft magnetic materials can result in excellent energy products-comparable to those from rapid solidification processing routes-in powder composites. The flexibility in manufacturing this allows should provide many possible permanent magnet applications.
Nanocrystalline soft magnetic materials have the lowest energy losses of any material. While problems such as mechanical brittleness remain, these materials promise to replace existing transformer core materials for power applications. The U.S. research and industrial effort in these materials lags the efforts in Japan.