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Development of Composite Nano Composite Magnets
Development of Composite Nano Composite Magnets
RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece
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The paper reviews the recent efforts to fabricate composite magnets with hard and soft magnetic
components or with two hard magnetic components. Within the more traditional "top-down" approach,
the composite magnets were produced from isotropic nanocrystalline precursors. Texture was developed
through a hot plastic deformation. The explored systems included the Nd(Pr)-Fe-B, Sm-Co and Sm-Fe-N
hard magnetic components. The other, "bottom-up" approach consists of the assembly, alignment and
consolidation of separate hard and soft particles. Anisotropic Sm-Co nanoparticles can be produced via
surfactant-assisted high-energy milling. A uniform distribution of soft phase can be achieved via coating
of the hard magnetic particles with chemically synthesized Fe nanoparticles.
Contact author: George C. Hadjipanayis, University of Delaware, 217 Sharp Lab, Newark, DE 19716,
U.S.A., Fax: 1-302-831-1637, Phone: 1-302-831-6289, E-mail: hadji@udel.edu.
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Original manuscript, Proceedings of 20th International Workshop on
RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece
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Original manuscript, Proceedings of 20th International Workshop on
RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece
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Original manuscript, Proceedings of 20th International Workshop on
RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece
__________________________________________________________________________________________________
complementary to the exchange coupling, the Fig. 5(a)]. In a good agreement with the theory
way to relax the restrictions for the size of soft for magnetostatically coupled composites [9],
magnetic components. Unfortunately, the the Fe addition markedly increased the
magnetostatic interaction places high saturation magnetization, but not the remanence.
requirements for the coercivity of the hard While the reaction between the RCo5 and Fe
magnetic phase, which must be high enough to components must produce the Fe-rich (and
withstand the stray fields of the soft phase magnetically soft) R2(Co,Fe)17 phase, the
[9,10]. moderately hard Sm2Co17 phase forms at the
One underestimated problem with the die- boundaries of the Co inclusions in the
upset composites made from R-rich R-Fe-B SmCo5/Co composites, shown in Fig. 6. Such
alloys and Fe(Co) is that during the hot SmCo5/Sm2Co17/Co composite magnets exhibit
deformation the liquid R-rich phase readily an increased remanence [Fig. 5(b)], and they
reacts with the Fe(Co) phase changing both the may offer us at least two interesting
amount of the Fe(Co) phase and the average
composition of the R-Fe-B matrix [10]. When
the addition of 2 - 3 wt. % Fe (by deposition
through sputtering onto the hard particles)
reportedly increased 4πMr of the die-upset Nd-
Fe-B magnet from 13 to 15 kG [11], one should
attribute this not to the higher magnetization of
the Fe phase (3 wt.% Fe can add to the total
magnetization only about 0.25 kG) but rather to
changes in the Nd-Fe-B component.
The high reactivity of the R-rich phase also
makes it very susceptible to oxidation during
milling and, therefore, complicates refinement Fig. 5. Demagnetization curves of hot-
of the R-Fe-B component in the R-Fe-B / deformed magnets made from high-energy
Fe(Co) composites [10]. Though not critical for milled RCo5 powder blended with 10 wt. % of
the effective exchange coupling, the size of hard (a) 10 μm Fe powder (deformation at 800 oC)
magnetic elements ultimately determines the and (b) 30 μm Co powder (deformation at 950
o
volume ratio of the soft component. It is quite C). Inset is rendered from the BSE SEM
obvious that the present "(BH)max challenge" micrograph.
cannot be answered by a composite magnet with
only a few percent of a high-magnetization soft
phase.
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Original manuscript, Proceedings of 20th International Workshop on
RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece
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opportunities. The microstructure of these
composites may be further optimized to take the
full advantage of the recently reported [16]
enhancement of the exchange coupling through
a graded interface. Moreover, if the emerging
2:17 phase follows the (partial) texture of the
parent 1:5 phase, the SmCo5/Co composites can
be developed into anisotropic Sm2Co17/SmCo5
magnets (the 2:17 phase itself is not susceptible
to the deformation-induced anisotropy [15]).
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Original manuscript, Proceedings of 20th International Workshop on
RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece
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3. Hard-soft magnets based on Sm2Fe17Nx
The Sm2Fe17Nx compound has a saturation
magnetization almost as high as Nd2Fe14B, but a
significantly higher Curie temperature and a
stronger magnetocrystalline anisotropy.
However, because it is less stable than the
mixture of SmN and Fe, the Sm2Fe17Nx can only
be obtained via nitrogenization of Sm2Fe17 and it
cannot be exposed to a temperatures greater than
600 oC. In reference [12], we pointed out that in
composite magnets made from Sm2Fe17Nx and a
soft magnetic phase, the latter may
simultaneously serve as a metal binder. The hot- Fig. 10. BSE SEM micrograph of Sm2Fe17Nx /
pressed Sm2Fe17Nx/Fe0.65Co0.35 composites Fe65Co35 composite consolidated at 570 oC
indeed showed considerably higher absolute and from blended Sm2.1Fe17 and (Fe0.65Co0.35)89N11
relative densities. powders. Location of nitrogen was found with
We have found that certain Co-substituted Fe XRD and TMA.
nitrides may provide nitrogen for synthesis of
Sm2Fe17Nx in such composites during the in situ nitrogenization. The more ductile Fe-
consolidation. The thermal gravimetric (TG) Co phase fills the space between the hard
scans in Fig. 9 show that decomposition of the Sm2Fe17Nx particles, resulting in a dramatic
Sm2.1Fe17N2.7 alloy starts at 600 oC (Sm2Fe17N≈3 increase of the density [12]. Of course, this
releases 1/3 of its N atoms when it dissociates merely demonstrates the concept; a much finer
into SmN and Fe), whereas the microstructure and a textured hard phase are
(Fe0.65Co0.35)89N11 alloy releases N at 450 oC required for the development of advanced
(the Co-free Fe89N11 does this only at 670 oC). permanent magnets.
Thus, in the Sm2Fe17/(Fe0.65Co0.35)89N11
composite, the N atoms released during 4. Nano-assembled composite magnets
decomposition of (Fe0.65Co0.35)89N11 can 4.1. Coating hard magnetic particles with high-
interstitially modify the Sm2Fe17 compound. magnetization nanoparticles
Fig. 10 shows the microstructures of the It is rather difficult to form thin continuous
Sm2Fe17Nx/Fe-Co composite obtained through layers of a soft magnetic phase by simply
blending the hard magnetic powders with the
much finer soft particles: distribution of the
smaller particles will be determined by the voids
between the larger particles. The natural solution
to this problem would be to form the desired
thin layers in advance, by coating the particles
while they are still separate. Different coating
techniques have been suggested for the
fabrication of nanocomposite magnets [11,18-
20]. We focus our efforts on coating the hard
magnetic particles with the Fe(B) nanoparticles
synthesized by chemical reduction of FeCl2 with
NaBH4 [20].
To perfect the coating technique we used the
Fig. 9. TG (heating) scans for ground Sm-Fe- model systems of Cu particles coated with the
N alloy and mechanically alloyed Fe-N and Fe nanoparticles. Cu powders with particle sizes
Fe-Co-N powders. ranging from 1 to 100 μm were immersed in the
reaction bath during the synthesis of Fe
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Original manuscript, Proceedings of 20th International Workshop on
RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece
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Original manuscript, Proceedings of 20th International Workshop on
RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece
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ONR, DOE and NSF.
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Original manuscript, Proceedings of 20th International Workshop on
RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece
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