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RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece
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Abstract. This paper presents research results reported in the past two years on high performance
Sm-Co permanent magnets. The work discussed is organized in two parts: (1) Sm-Co based bulk
permanent magnets referring to results on various magnetic and structural studies and new
achievements in the fabrication of (i) Sm(Co,Fe,Cu,Zr)z magnets with almost zero reversible
temperature coefficient of residual induction, (ii) Sm(Co,Fe,Cu,Zr)z magnets with increased
electrical resistivity, and (iii) Sm-Co bulk nanocomposites and (2) Sm-Co based ribbons,
nanoparticles and nanocomposite powders, for potential small scale applications or consolidation
into bulk specimens, referring to the latest results on their synthesis and characterization.
Contact author: M. Marinescu, Electron Energy Corporation, 924 Links Ave, Landisville, PA
17538, USA; tel: 717 898 2294; fax: 717 898 0660; mmarinescu@electronenergy.com
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1
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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measurements) for the temperature variation magnets which have a high resistivity due to
between -50 oC and 150 oC. Values of Br the insulation effect of polymer binders, but
exceeding 9 kG and Hk of over 20 kOe for in general the operating temperature is
some compositions (Hk is the dramatically limited by the polymer
demagnetization field at which Br is softening above 200 oC. Recently2, fully
decreased by 10%; Hk is a measure of loop dense composite magnets were produced by
squareness) allowed for excellent maximum sintering blends of Sm(Co,Fe,Cu,Zr)z
energy products (BH)max of 18-20 MGOe at magnet powder precursors and small
room temperature1. Figure 1 depicts the amounts of CaF3 powders. The resistivity of
demagnetization curve at different the magnets with 2.5 wt% CaF3 increased by
temperatures for a selected magnet 30% whereas the magnetic performance was
composition with the ratio of the rare earth only slightly altered: Br = 10.8 kG, Hci > 25
elements Gd/Er/Sm = 30/26/44 and TM/RE kOe, (BH)max = 27.1 MGOe. It was found
ratio z = 6.90. that some amount of Sm diffuses into the
CaF3 inclusions upon processing the magnet
at high temperatures. However, this can be
compensated with excess Sm in the magnet
powder precursor. A much higher increase
in the electrical resistivity of ~ 1000 µΩ⋅cm
was achieved in “glass-bonded” anisotropic
Sm(Co,Fe,Cu,Zr)z / B2O3 magnets produced
by hot pressing at 475 oC, which is slightly
above the melting point of B2O3. In this
case, the Sm(Co,Fe,Cu,Zr)z powder had
already developed hard magnetic properties
and B2O3 acted as a binder. The relatively
low-temperature consolidation preserved the
high coercivity of the Sm(Co,Fe,Cu,Zr)z
magnet powder, but the residual induction
Figure 1 Demagnetization curves at different was decreased due to a lower density and led
temperatures for (Sm,Gd,Er)(Co,Fe,Cu,Zr)z magnets
to a (BH)max of 8 MGOe.
processed by isostatic pressing, sintering at 1210 oC,
solution treatment at temperatures in the range of
1195- 1200 oC and aging at 815 oC for 36h. Effect of oxygen and residual carbon in
sintered Sm(Co,Fe,Cu,Zr)z magnets
For applications above 400 oC,
Sintered Sm(Co,Fe,Cu,Zr)z magnets with Sm(Co,Fe,Cu,Zr)z magnets need to be
increased electrical resisitivity coated usually by Ni plating. A recent study3
The electrical resistivity of Sm-Co reported results of the in-air oxidation
magnets typically ranges from 37-77 process of uncoated Sm(Co,Fe,Cu,Zr)z
µΩ⋅cm, while of Nd-Fe-B magnets is about magnets at temperatures between 300 oC and
0.14 µΩ⋅cm. Magnets with increased 600 oC. The respective findings suggest that
electrical resistivity are needed in permanent the oxides layers formed on the surface,
magnet motors and high speed power which is depleted in Sm, are CuO, Co3O4
generators in order to reduce eddy current and CoFe2O4. These layers do not exceed 15
losses. One of the solutions is to use bonded µm and their effect on magnetic properties is
negligible. A so-called internal oxidation
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2
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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zone was found to follow the above oxide many years6. Magnets with a lower
layers and to consist of a CoFe matrix with a operating temperature (larger Fe content)
Sm-rich oxide and Cu and Co precipitates. showed more pronounced losses after
This zone grows parabolically in time exposure at 300 oC in air, while the Ni and
inwards the bulk body of the magnets and Al coated high temperature magnets able to
can be more damaging to the magnetic operate up to 550 oC showed almost no
properties. losses after the initial thermal stabilization,
Residual carbon in Sm(Co,Fe,Cu,Zr)z as shown in Figure 2.
magnets may become an important issue
when the magnets are produced from
powder milled in alcohol or consolidated
with an organic binder aid (especially in the
case of small specimens which are otherwise
difficult to be formed). A study4 showed that
the magnetic properties of the magnets start
to deteriorate when the carbon content is
above 0.1 wt%, and even extinguish for 0.43
wt% carbon. It appears that carbon reacts
with Zr forming ZrC, possibly during
sintering. The typical cellular microstructure
of Sm(Co,Fe,Cu,Zr)z magnets appears to be
highly distorted in the specimens containing Figure 2 Thermal stability at 300oC in air for more
0.43 wt% carbon and have much larger non- than three years, of various Sm(Co,Fe,Cu,Zr)z
magnets with an operating temperature of 250 oC to
uniform cells while the amount of the 1:5 550 oC.
cell boundaries is reduced. The widely-
accepted mechanism of Cu diffusion to the
1:5 cell boundary and hence the 1.0
development of coercivity intermediated by Sm-Co Magnet Sample
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4
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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most interesting results are from the addition these methods. Thus, a recent study10 was
of In that results in the precipitation of a focused on Smx(Co,Fe,Mn)100-x (x= 9-16.7
Sm-Co-In (assumed) non-magnetic phase at%) high energy ball milled powder and
with a low melting temperature (1070oC) consolidated magnets prepared by hot
and fairly good wetting behavior, able to pressing. The powder and magnets were
support low temperature liquid phase isotropic and, for a slightly
sintering for achieving almost full density. overstoichiometric composition, the (BH)max
Figure 5 shows the morphology of this was 15.6 MGOe for the annealed
specimen along the fractured section in the Sm11(Co0.85Fe0.075Mn0.075)89 powder and 15.7
micrograph taken by scanning electron MGOe for Sm13(Co0.7Fe0.25Mn0.05)87 hot
microscopy in back scattering mode and pressed magnets with a 88% density.
distribution of elemental In. Although the Although the level of (BH)max was in the
grains are considerably large, it appears that range of that obtained for the Fe substitution
the addition of In leads to an increased Hci alone, the addition of Mn brings a better
of up to 8 kOe in structural stability of the magnets which can
Sm12.5(Co0.85Fe0.11Mn0.04)86In1.5 magnets be hot pressed at temperatures as high as
sintered at 1075oC and annealed at 1000oC 750- 800 oC without the precipitation of
with a subsequent quenching. The unwanted phases (i.e. 1:3, 1:2 phases). The
remanence of the best specimens did not variation of the hysteresis parameters as a
exceed 9 kG, which limits the practical use function of the annealing temperature
of these magnets. between 550 oC and 800 oC for
Smx(Co0.85Fe0.075Mn0.075)100-x is given in
(a) (b) Figure 6. The efforts to develop
nanocomposite counterparts by shifting the
composition towards a lean-Sm content
were not successful in terms of the achieved
levels of (BH)max. What is interesting to note
is that a low devitrification annealing
temperature (600 oC) may lead to a fine 1:7 /
Figure 5 (a) BSE SEM image of a fractured surface bcc exchange coupled microstructure that
of Sm12.5(Co0.85Fe0.075Mn0.075)86In1.5 magnet sintered
exhibits a high 4πMr = 11.4 kG but the
at 1075 oC and (b) indium elemental map for the
selected area. respective temperature is apparently not
enough to develop a reasonable Hci. For
It has been shown in early studies9 that higher annealing temperature (800 oC),
the combined Mn and Fe substitution for Co which results in an Hci ~ 7 kOe, the
in Sm2Co17 sintered magnets with the exchange coupling is altered as a
rhombohedral Th2Zn17-type structure results consequence of microstructure coarsening
in an increase of both anisotropy constant K1 and a pronounced kink appears in the
and saturation magnetization Ms. Moreover, demagnetization curve.
a higher anisotropy can be obtained in the Bulk nanocrystalline SmCo7-xHfx have
disordered TbCu7-type structure of Sm2Co17 been produced with 98% full density by
phase, which is mostly favored when spark plasma sintering of the precursor high
applying non-equilibrium synthesis methods energy ball milled powder11. However, the
such as rapid quenching or mechanical dramatic increase of Hci with the Hf addition
alloying or upon devitrification annealing of up to 20.8 kOe for SmCo6.08Hf0.2 is hindered
non-crystalline precursors synthesized with by values of 4πMr below 6 kG. Hysteresis
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5
Original manuscript, Proceedings of 20th International Workshop on
RARE EARTH PERMANENT MAGNETS AND THEIR APPLICATIONS, Sept. 8-10, 2008, Crete, Greece
_____________________________________________________________________________________________
loops for bulk nanocrystalline specimens melt-spun binary SmxCo100-x alloys with x
with different Hf content is given in Figure ranging from 4 to 16 was also recently
7. revisited12. For the ribbons spun at 40 m/s
wheel speed, 1:7 and fcc/hcp Co phases
were observed up to x = 12. As expected, Co
dendrites precipitate at low Sm content
while the microstructure was eutectic when
x = 8. For compositions with x = 6 to 10, the
Co precipitates are scaled to less than 50 nm
with an elongated (rods) morphology and
the matrix consists of almost submicron 1:7
grains. For Sm-rich compositions the
structure becomes coarser. The formation of
1:5 phase leads to the increase of Hci up to
9.3 kOe, but the maximum energy product is
expected to be low due to modest
magnetization values.
Similar with the case of Fe-Pt and Sm-
Fe-N systems for which the magnetic
properties are dependent on the structural
Figure 6 Effect of annealing temperature on intrinsic
ordering, the intrinsic coercivity and
coercivity, remanent magnetization and maximum magnetization / demagnetization processes
energy product of high-energy milled and annealed in Sm-Co melt-spun ribbons can be
Smx(Co0.85Fe0.075Mn0.075)100-x alloys. correlated with the order-disorder phase
transformations. In a recent work13, the
small addition of C and Nb to the base Sm-
Co composition with a stoichiometry in the
neighborhood of 2:17 phase is not
necessarily accounted for the relative high
Hci (7.85 kOe) as developed through
microstructure refinement. The
microstructure of (Sm12Co88)94Nb3C3
ribbons spun at 40 m/s is reported to consist
of ~100 nm 1:7 grains and ~ 10 nm Co
precipitates (however, it may be hard to
distinguish fcc Co from fcc NbC). NbC
precipitates at the grain boundaries upon
Figure 7 Hysteresis loops of the bulk nanocrystalline annealing, part of the 1:7 phase transforms
SmCo7−xHfx magnets produced by spark plasma
sintering (from ref. 11).
into the long-range ordered 2:17R phase and
Hci is increased to a little over 9 kOe. The
III. Sm-Co ribbons, nanoparticles and authors suggest that the increased role of
nanocomposite powders domain wall pinning observed is a result of
Sm-Co melt spun ribbons the presence of antiphase defects, APD, with
a size of ~ 8 nm. The interface between the
The topic of the evolution of defects and the matrix acts as domain wall
microstructure and magnetic properties in pinning sites in a way similar to the
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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
_____________________________________________________________________________________________
Sm(Co,Fe,Cu,Zr)z systems with a 2:17 /1:5 annealing of core/shell structured Co/Sm2O3
cellular microstructure. nanoparticles17. The intrinsic coercivities at
The dramatic effect of microstructure room temperature were 8 kOe and 1.4 kOe,
refinement14 with the precipitation of RCoC2 respectively.
carbides that may act as grain growth
Isotropic SmCo5/Fe nanocomposite
inhibitors was achieved in Sm-(Co,Fe)-C
powders were synthesized18 by high
and Sm-(Co,Fe,Mn)-C melt spun ribbons
temperature reductive annealing of Fe3O4
and is shown in Figure 8. The combined
nanoparticles embedded in a SmCo-
addition of Mn and C did contribute to an
hydroxide matrix. The general trend of the
intrinsic coercivity of Hci= 11.7 kOe but the
magnetic properties of this isotropic
largest (BH)max = 14.7 MGOe was reached
composite powder is typical: with increasing
with a Mn-free Sm13(Co0.75Fe0.25)82.5C4.5 amounts of Fe nanoparticles incorporated
stoichiometry. Stoichiometry and quenching
into SmCo5 nanostructured matrix,
rate dictate the phase composition and, up to magnetization increases and intrinsic
a certain extent, C suppresses the formation
coercivity declines. Figure 9 shows the
of the stable 2:17R in favor of the disordered
structure of the nanocomposite powder
metastable 1:7H14. Another atomic specie
together with the hysteresis of the Fe-free
know to stabilize the 1:7 structure and
SmCo5 and SmCo5Fe1.5 nanocomposites.
increase the anisotropy field is Ti whose
addition to SmCo7 lead to a Hci of 9.7 kOe
in SmCo7.1Ti0.4 ribbons spun at high wheel (a) (b)
speed15. However, the exposure at 750 oC
starts to transform 1:7 into 2:17.
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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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deposition conditions lead to enhanced 5. M. S. Walmer, C. H. Chen, M. H.
remanent magnetization from 10.5 kG to 11 Walmer, S. Liu, and G. E. Kuhl, IEEE
kG with Fe-nanoparticle coating while the trans. Magn. 36 (2000) 3376
squareness of the loop and Hci>25 kOe are 6. J. F. Liu, P. Vora, P. Dent, M. Walmer, C.
also preserved. Upon hot pressing, the Fe Chen, J. Talnagi, S. Wu and M. Harmer,
nanoparticles transform into a nanolayer Proc. of Space Nuclear Conference 2007,
distributed around the original core powder. Boston, Paper 2036
However, some local agglomeration of Fe 7. M. Q. Huang, Z. Turgut, B.M. Ma, Z. M.
still occurs. The magnetic properties of the Chen, D. Lee, A. Higgins, C. H. Chen, S.
consolidated composite powders are yet to Liu, S. Y. Chu, J. C. Horwarth, and R.T.
be optimized. Figure 10 shows SEM Fingers, J. Appl. Phys. 103 (2008)
micrographs of composite 07E134
Sm(Co0.699Fe0.213Cu0.064Zr0.024)7.4 / nano-Fe 8. A. M. Gabay, M. Marinescu, J. F. Liu,
free powder and hot pressed magnets. and G. C. Hadjipanayis, J. Appl. Phys.
(b)
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Figure 10 SEM micrograph of a composite 07E125
Sm(Co0.699Fe0.213Cu0.064Zr0.024)7.4 / nano-Fe free
powder (a) and (b) and hot pressed magnet (c).
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8 (a)