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Original manuscript, Proceedings of 20th International Workshop on


Sm-Co and Pr-Fe-B Magnets with Increased Electrical Resistivity

M. Marinescu1, A. M. Gabay2, S. Kodat1, J. F. Liu1, G. C. Hadjipanayis2

Electron Energy Corporation, Landisville, PA, USA
Department of Physics and Astronomy, University of Delaware, Newark DE, USA

Abstract. Fully dense composite magnets produced by sintering blends of Sm(Co,Fe,Cu,Zr)z and
CaF3 precursor powders had an electrical resistivity 30% higher than conventional
Sm(Co,Fe,Cu,Zr)z magnets. The magnetic performance was only slightly altered with the
addition of 2.5 wt% of CaF2: Br = 10.8 kG, Hci > 25 kOe, (BH)max = 27.1 MGOe. A much higher
electrical resistivity of up to ~ 1000 µΩ⋅cm was achieved in “glass-bonded” Sm(Co,Fe,Cu,Zr)z /
B2O3 magnets produced by hot pressing at 475 oC. The low-temperature consolidation preserved
the high intrinsic coercivity of the Sm(Co,Fe,Cu,Zr)z magnet powder, but the residual induction
was decreased due to a lower density.
Fully dense composite magnets based on Pr-Fe-B and other rare earth fluoride powders were
produced by hot pressing and die upsetting the precursor blends. The overstoichiometric
composition of Pr14.5Fe79.5B6 powders from melt-spun precursors allowed, upon the thermal
processing with NdF3, DyF3 and CaF2 fine powders, the formation of a morphology where the
fluoride surrounded the Pr14.5Fe79.5B6 component in the magnet. The addition of fluorides
increased the resistivity by more than 200% and improved the intrinsic coercivity to values
above 15 kOe with a slight reduction of residual induction in the range of 10.5- 11 kG.

Keywords: Sm-Co magnets, Pr-Fe-B magnets, electrical resistivity, die upsetting, fluorides,

Contact author: M. Marinescu, Electron Energy Corporation, 924 Links Ave, Landisville, PA
17538, USA; tel: 717 898 2294; fax: 717 898 0660;

I. INTRODUCTION magnetic flux is reduced due to the low

Eddy current losses represent one of the density. Besides polymers, other insulators
important considerations in the design of such as fluorides and oxides of Li, Na, Mg,
motors and high speed power generators. Ca, Ba and Sr were shown2 to increase the
Reduction of eddy current losses in rotor electrical resistivity of the rare earth (RE)
permanent magnets is typically achieved by magnets to a level sufficient for practical use
surface engineering, i.e. by segmenting the in regard to their magnetic performance. A
magnet elements. In a much simpler fashion, recent article3 reported a high electrical
the increase of resistivity of permanent resistivity (1.4 mΩ⋅cm) of isotropic hot
magnets could decrease the eddy current pressed Nd-Fe-B magnets synthesized from
losses through a simple inverse Nd-Fe-B powders coated with a 200 nm Nd
proportionality1. Bonded magnets have high fluoride layer grown using a fluoride
resistivity due to the insulation effect of solution. Sm-Fe-N / ferrite composite
polymer binders, but the operating magnets with a resistivity of 4 mΩ⋅cm were
temperature is dramatically limited by the produced from ferrite plated Sm-Fe-N
polymer softening above 200 oC while the powders4 and consolidated to almost full

Original manuscript, Proceedings of 20th International Workshop on
density by die pressing and explosive The phase composition of the composite
consolidation technique. magnets was examined by powder X-ray
This work presents our results on Sm-Co diffraction (XRD) with the Cu-Kα radiation.
and Pr-Fe-B permanent magnets with The microstructure and microchemistry was
increased electrical resistivity by the investigated by scanning electron
addition of boron oxide, calcium fluoride, microscopy (SEM) with a JEOL JSM-6330F
neodymium fluoride and dysprosium instrument equipped with an energy
fluoride. dispersive X-ray (EDX) detector. The
magnetic measurements were done with a
II. EXPERIMENT Lakeshore vibrating sample magnetometer
Sm-Co based powders with a particle size (VSM) at room temperature and also at
of about 2.5 µm were prepared by milling higher temperatures up to 240 oC for Sm-Co
the precursor alloys cast by induction based magnets. Alignment and saturation of
melting from pure elements. The final the composite magnets was done in fields of
composition was controlled and optimized up to 100 kOe. The density of the composite
with respect to the loss of Sm through specimens was calculated from the
oxidation and evaporation by mixing Sm-Co geometrical dimensions. The resistivity was
powders with two stoichiometries: one mix measured by the four probe technique.
consisting of Sm(Co0.70Fe0.21Cu0.06Zr0.03)7.4
and Sm(Co0.66Fe0.24Cu0.07Zr0.03)4.9 and a
second mix consisting of III. RESULTS AND DISCUSSION
Sm(Co0.66Fe0.27Cu0.05Zr0.02)7.7 and A. Fluoride-Added Sintered Sm-Co
Sm(Co0.62Fe0.30Cu0.06Zr0.02)4.9. CaF2 powder The optimum amount of Sm-rich
was added to the Sm-Co mixed powder by Sm(Co0.66Fe0.24Cu0.07Zr0.03)4.9 powder
simple blending in amounts of 2.5 and 5 needed to be added to base
wt%. The Sm(Co,Fe,Cu,Zr)z / CaF2 blends Sm(Co0.70Fe0.21Cu0.06Zr0.03)7.4 powder in
were consolidated into blocks by isostatic order to achieve the best hard magnetic
pressing. The green compacts were performance in the sintered magnets is about
subjected to the conventional thermal 7.5 wt%. In order to preserve a high Hci of
processing consisting of sintering in H2 at 25 kOe after adding 2.5 - 5.0 wt.% CaF2, the
1195 oC, solution treatment at 1175 oC and amount of the Sm-rich powder had to be
aging at 840 oC. increased up to 19 wt.%, as it is shown in
Some Sm(Co,Fe,Cu,Zr)z anisotropic Fig. 1. By increasing the level of CaF2
powder with already developed hard addition to 5 wt.%, the remanence decreases
magnetic properties produced by milling below the theoretically expected 10.2 kG.
EEC 2:17-27 and EEC 24-T400 non- The Sm-Co composition optimized by
saturated magnets5 were blended with B2O3 mixing Sm(Co0.66Fe0.27Cu0.05Zr0.02)7.7 and
powder in amounts of 2.5, 5 and 10 wt%. 16 wt% of Sm(Co0.62Fe0.30Cu0.06Zr0.02)4.9
The blends were aligned and hot pressed at leads to very good magnetic properties when
475 oC, slightly above the melting point of sintered with small amounts of CaF2,
B2O3 (450 oC). properties which are maintained at elevated
Pr14.5Fe79.5B6 melt-spun ribbons were temperatures as depicted in Fig. 2. The best-
ground and blended with 5 wt% of CaF2, achieved magnetic properties at room
NdF3 and DyF3 powders. The blends were temperature with 2.5 wt% CaF2 are: Br =
consolidated by hot pressing at 650oC and 10.8 kG, Hci > 25 kOe, (BH)max = 27.1
die-upset at 750oC. MGOe.

Original manuscript, Proceedings of 20th International Workshop on
fully dense Sm(Co,Fe,Cu,Zr)z magnets (8.4
Structure investigation showed that CaF2
does not dissociate during the thermal
processing of the magnets. The X-ray
diffraction patterns in Fig. 3 are identified
and belong to the Th2Zn17 and CaF2
structure types. However, detailed
compositional analyses by EDX (not shown)
revealed that a small amount of Sm diffuses
into the CaF2, effectively reducing the ratio
z in the Sm(Co,Fe,Cu,Zr)z matrix and
therefore extra amount of Sm was
introduced with the Sm-rich powder.
Figure 1 Demagnetization curves of magnets The resistivity of the composite
synthesized from Sm(Co0.70Fe0.21Cu0.06Zr0.03)7.4 with
different percentage of added Sm-rich
Sm(Co,Fe,Cu,Zr)z / CaF2 magnets was found
Sm(Co0.66Fe0.24Cu0.07Zr0.03)4.9 and CaF2 powders. to increase up to slightly over 90 μΩ⋅cm
which is 30% more than that of the regular
Sm(Co,Fe,Cu,Zr)z magnets.

Figure 3 X-ray diffraction analysis shows the

existence of Sm2(Co,Fe)17 and CaF2 phases in
Sm(Co,Fe,Cu,Zr)z / CaF2 composite magnet sintered
at 1200 oC.

Figure 2 Magnetic properties of optimized fully

B. Glass-Bonded Sm-Co
dense Sm(Co0.66Fe0.27Cu0.05Zr0.02)7.7 + 16 wt%
Sm(Co0.62Fe0.30Cu0.06Zr0.02)4.9 / CaF2 composite A much more dramatic increase of
magnet with the resistivity increased 30% compared electrical resistivity was obtained for
to the commercial Sm-Co 2:17 magnets. These composite magnets synthesized from blends
magnets are able to operate at temperatures of 240 oC of Sm(Co,Fe,Cu,Zr)z powders with already
and above.
developed hard magnetic properties and
B2O3 powder. The electrical resistivity for
The density of the composite specimens was samples with 2.5 wt% of B2O3 exceeded
97% of the theoretical value calculated from
1000 µΩ⋅cm, which is almost 12 times
the density of CaF2 (3.18 g/cm3) and that of
higher compared to the conventional

Original manuscript, Proceedings of 20th International Workshop on
sintered counterparts. The larger the (BH)max morphology that is beneficial for increasing
of the precursor magnets, the more sensitive the resistivity. Some Sm(Co,Fe,Cu,Zr)z /
the powder is to milling with respect to B2O3 specimens showed a resistivity as high
preserving the hard magnetic properties. as 6000 µΩ⋅cm, due to a high porosity
Only high-coercivity high-temperature determined by a less efficient hot pressing
Sm(Co,Fe,Cu,Zr)z bulk magnet specimens procedure and larger particle size of magnet
(EEC 24- T4005) were able to preserve a powder. Surprisingly, the addition of 5 or 10
high coercivity upon milling to 10 µm wt% of B2O3 does not reduce the porosity.
powder. Smaller particle size that may
ensure a better packing factor and higher
density of the composite compacts, could
retain neither magnetization (due to the
lattice distortions and increased surface to
volume ratio and surface oxidation) nor
intrinsic coercivity (due to the defects
introduced into the cellular microstructure)6.
EEC 24-T400 powders were also able to
withstand temperatures of 475 oC employed
in the hot-pressing process. However, these
high temperature bonded magnets showed a
low density and hence a lower residual
induction of 5.85 kG (Fig. 4); the best
achieved density was 6.10 g/cm3.

Figure 5 (a) backscattered electron SEM micrograph

and (b) EDX map for oxygen showing dielectric
boron oxide and few samarium oxide inclusions
within the EEC 24- T400 / B2O3 (2.5 wt%) “glass-
bonded” magnet.

C. Fluoride Added Die-Upset R-Fe-B

Die-upset magnets made of blended
Pr14.5Fe79.5B6 and CaF2 / NdF3 / DyF3
powders showed almost full density with
values of 7.02, 7.40 and 7.37 g/cm3 for 5
wt.% of CaF2, NdF3 and DyF3, respectively.
Figure 4 Demagnetization curve of EEC 24- T400 / The accurate detection of fluorine itself with
B2O3 “glass-bonded” magnets with electrical EDX was not possible since its major energy
resistivity of 1138 µΩ⋅cm: Br = 5.85 kG, Hci > 30 line is overlapped with one of the Fe lines.
kOe, Hk = 7.67 kOe, (BH)max = 8.06 MGOe.
However, EDX analyses revealed that upon
hot pressing and die upsetting, Ca, Nd and
The specimens showed an improved
Dy are driven throughout the whole volume
mechanical strength which will be further
of the composite by the Pr-rich phase, which
investigated. The oxide was found to be
is in the molten state at the hot pressing and
distributed fairly uniformly around the
die upsetting temperature. A so called “grain
magnet powder particles (Fig. 5),
boundary diffusion process” was also

Original manuscript, Proceedings of 20th International Workshop on
reported7 in which the rare earth atoms from IV. CONCLUSION
their fluorides are able to diffuse through the Composite sintered Sm(Co,Fe,Cu,Zr)z /
Nd-rich phase from the surface of the Nd- CaF2 magnets were produced at almost full
Fe-B magnets inside. A similar process density with very good hard magnetic
happens in our case when the Pr-Fe-B properties and the electrical resistivity is
powder is mixed with the fluoride powder. 30% higher compared to the metallic-only
However, assuming that the fluorides do not counterparts. Bonded Sm(Co,Fe,Cu,Zr)z /
decompose entirely, the morphology is B2O3 magnets had a high electrical
beneficial for the electrical insulation of the resistivity of ~ 1000 µΩ⋅cm and high
conductive matrix. On the downside, the coercivity, but a residual induction of only
addition of CaF2 seems to lead to 5.85 kG due to the reduced density. Pr-Fe-B
development of fine internal cracks during / fluorides composite magnets prepared by
hot pressing, whereas the composites with hot pressing and die upsetting show an
DyF3 showed a certain tendency towards electrical resistivity twice as high as
cleavage. conventional Pr-Fe-B magnets, while
maintaining a good hard magnetic
performance. The addition of CaF2, NdF3
and DyF3 was found to enhance the intrinsic
coercivity. NdF3 improves the squareness of
the demagnetization curve of Pr-Fe-B
magnets prepared by hot pressing and die

This work was supported by US DoE
grant DE-FG02-07ER86308.

1. D. Ishak, Z.Q. Zhu and D. Howe, IEEE
Figure 6 Demagnetization curves for die-upset Trans. Magn. 41, 9 (2005) 2462
magnets made of blended Pr14.5Fe79.5B6 and CaF2 / 2. US patent 5858124 (1999)
NdF3 / DyF3 powders. The fluoride additions increase
3. M. Komuro, Y. Satsu, Y. Enomoto and H.
the electrical resistivity of the magnets at least two
times. Koharagi, Appl. Phys. Lett. 91 (2007)
The Pr-Fe-B / fluorides composites have 4. N. Imaoka, Y. Koyama, T. Nakao, S.
an electrical resistivity at least two times Nakaoka, T. Yamaguchi, E. Kakimoto,
higher as compared to the 2:14:1 magnets. M. Tada, T. Nakagawa and M. Abe, J.
Values of 470 - 780, 290 - 310 and 680 - Appl. Phys. 103 (2008) 07E129
780 µΩ⋅cm were obtained for Pr-Fe-B / 5% 5. EEC brochure available at
CaF2, Pr-Fe-B / 5% NdF3 and Pr-Fe-B / 5%
DyF3 samples, respectively. The addition of 6. Y. Zhang, Q. Zheng, G. C. Hadjipanayis,
fluorides causes an increase in Hci, and J. Appl. Phys. 97 (2005) 10H107
NdF3, in particular, proves to be very 7. K. Hirota, H. Nakamura, T. Minowa, and
favorable for improving the squareness of M. Honshima, IEEE Trans. Magn. 42, 10
the demagnetization curve, as seen in Fig. 6. (2006) 2909