Pr-Fe and Nd-Fe-based materials: A new class of high-performance

permanent magnets (invited)

J. J. Croat, J. F. Herbst, R. W. Lee, and F. E. Pinkerton
Physics Department, General Motors Research Laboratories. Warren. Michigan 48090-9055

We report the properties of a new class of high-performance permanent magnets prepared from
Nd-Fe-B and Pr-Fe-B alloys. Magnetic hardening is achieved by rapid solidification. Energy
products of these isotropic materials can exceed 14 MGOe with intrinsic coercivities of - 15 kOe.
X-ray and microstructural analyses indicate that the alloys exhibiting optimum characteristics
are comprised of roughly spherical crystallites, strongly suggesting that the coercivity mechanism
is of the single-domain particle type. The crystallites are composed of an equilibrium R-Fe-B
intermetallic phase having tetragonal symmetry, and the stability of this phase with respect to
other rare earths and other metalloids has been investigated.
PACS numbers: 75.50.Ki, 75.30.Cr, 61.4O.Df, 81.40.Rs

INTRODUCTION all other experimental parameters constant. Magnetic mea-

Development of rare earth-iron-based permanent mag-
nets has been a long standing, long elusive goal. In the last
several years, however, prospects for producing magnets
from such materials have been greatly enhanced by the use of
rapid quench techniques. l -6 High coercivity, unachievable
by conventional powder metallurgy methods, has been ob-
tained either by crystallization of an amorphous precursor
or by direct quenching from the melt. In a recent letter7 we
described the hard magnetic properties of melt-spun Nd-Fe-
B alloys. A maximum energy product of 14.1 MGOe, the
largest value ever reported for a light rare earth-iron magnet,
was attained. Here we discuss in detail our investigation of
these and related materials.
EXPERIMENTAL METHODS
Starting ingots were prepared by arc melting commer-
cially available constitutents. Portions of these ingots were
then melt spun in an argon atmosphere by ejecting molten
alloy through an orifice in a quartz crucible onto the edge of
a rotating substrate disk. The quench rate was varied by
changing the substrate surface velocity Us while maintaining
surements were made on powdered and compacted speci-
mens with a vibrating sample magnetometer (H <: 19 kOe).
Since both the coercivity and remanence are strongly depen-
dent on the maximum magnetizing field, demagnetization
data were taken after premagnetizing the samples in a pulsed
field of ~45 kOe.
MAGNETIC PROPERTIES
Figure 1 displays energy product (BH )max vs Us for a
Ndo.135 (Fe o.945 B0.Q55 )0.865 alloy. A maximum energy pro-
duct of 14.0 MGOe was achieved at a quench rate corre-
sponding to Us = 19 m/s. Optimum values of 12-14 MGOe
are observed over a relatively narrow Us interval of 16-20 ml
s. (BH )max decreases rapidly at higher quench rates, falling to
negligible values for Vs ;;.30 m/s. Demagnetization behavior
as a function of substrate velocity is shown for several alloys
in Fig. 2; the Vs = 19 mls curve is very near the optimum
shape achieved for these magnetically isotropic materials.
M(kG)

NdO.135(Fe0945 BO.055)0.865

15r----r----~---,r----r----~--~
Vs = 19 m/s
14.0MG·Oe

I
I
10 I
Ql
Vs=14m/s 1/
o 6.9MG·Oe----..,.'
~
~
/
/

'"E" NdO.135(FeO.945BO.055' 0.865 /

/
/
£ /

!!? 5 ,// / ..- Ingot

- O.OMG·Oe
2
/ Vs=21.7m/s ~/
/ 2.2MG·Oei
,
/ / ,,
·15 ·10 ·5 o 5
H(kOe)
Vs (m/s'
FIG. 2. Room-temperature demagnetization curves for a
FIG. I. Room-temperature energy product (BH)max vs substrate velocity v, Ndo.l35 (Feo ••sBo.o,,)o,", ingot and four samples melt spun from it at the
for melt-spun Ndo m (Feo.94 , Bo.D" )0.'6' alloys. indicated substrate velocities [/,.

2078 J. Appl. Phys. 55 (6).15 March 1984 0021-8979/84/062078-05$02.40 © 1984 American Institute of Physics 2078
 10
(NdO.SRO.21o.135 (FeO.935 BO.0651o.S65
4 likely explanation for the low coercivities of the Sm, Th, and
2 non-negligible Hci observed for the alloy containing Gd,
-20 o 5
FIG. 3. Demagnetization curves for (Nd" g Ro2)0135 (Fe0935Bo06,)0865 al-
loys melt spun at the optimum rates.
Samples quenched at less than the optimum rate are charac-
terized by low first quadrant magnetization and low H ci ,
while those quenched faster than optimum have high mag-
netization and low coercivity. At the most rapid rates
(us> 30 m/s) the alloys exhibit glass-like behavior with only
a few hundred oersteds coercivity. Also shown in Fig. 2 is the
demagnetization curve of the homogenized arc-melted
ingot. This curve essentially represents the zero quench rate
limit; the coercivity is only - 200 Oe.
Results optimized with respect to quench rate are dis-
played in Fig. 3 for the (Ndo.8 Ro.2 )0. \35 (FeO. 935 Bo.065 )0.865
composition with R = La, Ce, Pr, Nd, Sm, Th, and Dy. The
Pr and Nd materials behave similarly, although Pr generally
provides higher intrinsic coercivity with lower remanence.
He; increases significantly for the Th and Dy alloys but is
accompanied by a drop in Br and, hence, energy product. It
is clear that La, Ce, and especially Sm additions substantial-
ly reduce H ci •
Figure 4 presents data for Ro.135 (Feo.935 Bo.065 )0.865 ma-
terials with R = La, Ce, Pr, Nd, Sm, Gd, Th, and Dy. Ex-
cepting the Pr and Nd compositions, all of the alloys exhibit
drastically reduced coercivity and energy product. This be-
havior is again especially surprising in the case of Sm, the
rare earth of choice in cobalt-based permanent magnets; the
maximum He; achieved for the Sm alloy is only 2 kOe. A
Dy materials is substantial reduction of the Curie tempera-
ture Tc from its -560 K value for the Nd-only alloy. The
which has zero orbital moment, is also unexpected since the
magnetic anisotropy is generally thought to be fundamental-
ly linked to the orbital moment of the rare earth ion. This
result raises the possibility that substantial anisotropy is gen-
erated by the Fe sublattice.
We have also examined the influence of glass-forming
elements other than boron. Ndo.135 (FeO.935 Meo.065 )0.865 sam-
ples having Me = C, Si, AI, Ge, and P were prepared and
melt spun over a range of substrate velocity. He; was below 1
kOe in every case, and similar results were found for the
cognate Pr-Fe-Me alloys.
CRYSTAL STRUCTURE AND PHASE OCCURRENCE
The materials having the largest energy products are
comprised chiefly of an equilibrium R-Fe-B intermetallic
compound. Although the stoichiometry is not known pre-
cisely, it is near R 2 Fe 14B. Preliminary analysis of x-ray data
on the Nd-Fe-B alloys indicates that the overall crystal
structure is tetragonal with lattice constants a = 8.8 A,
c = 12.2 A.. Four Nd 2 Fe l4B formula units in a cell ofthese
dimensions give a density of 7.6 g/cm J , which agrees with
the measured value.

10

RO.135 (Fe O.935 BO.0651o.S65

Pr /'

/ (c)
Vs=21.7m/s
/
/
/-Nd
I
J
I
-15 -10 -5 o 5 20 30 40 60
H(kOe)
21
FIG. 4. Demagnetization curves for Ro 135 (Feo "" Bo.06 , )0.86' materials melt FIG. 5. Cu Ka x-ray diffraction patterns for the Nd,,13S (Feo.94,Bo.0,,)086'
spun at the optimum rates. ingot (a) and three samples melt Spun from it (bHd).

2079 J. Appl. Phys., Vol. 55, NO.6, 15 March 1984 Croat eta!. 2079
E CeO.135 (FeO.935BO.065)0.865
'§ ingot
-e
!E.

TbO.135(FeO.935BO.065)0.865
ingot

20 30 40 50
28
FIG. 6. X-ray diffraction patterns for Ceo. 135 (FeD.935 B o.o65 )0 865 and
(Feo.935 Bo 065 )0.865 ingots.
Tho. 135

In Fig. 5 the x-ray diffraction pattern for a homog-

enized Nd o 135 (Feo935 Bo.065 )0.865 ingot is compared with pat-
terns for melt-spun samples prepared from it (Fig. 2 contains
the corresponding demagnetization curves). Although con-
siderable line broadening is evident in the spectrum of the
optimum-quenched (us = 19 m/s) specimen, there is a one-
to-one correspondence with the Bragg reflections of the
ingot, implying that the same phase is present in both alloys.
The patterns for the samples quenched at higher rates show
increasingly broader reflections, indicating a progressive re-
duction in the average crystallite size. The Us = 35 mls spec-
FIG. 7. SEM micrographs of regions near the free surface (top), middle, and
trum, dominated by a broad peak centered at 2e~40 0, is quench surface of a Ndo . 135 (Feo.945 Bo.055 )0.865 ribbon melt spun at v, = 19
characteristic of an amorphous or an extremely fine-grained mls (optimum).
crystalline microstructure.
X-ray analyses strongly suggest that the same tetra-
gonal phase forms with Ce, Pr, Nd, Sm, Gd, Tb, Dy, Er, or
Ho as the rare earth constituent. Diffraction patterns for
Ceo. \35 (Fe o.935 Bo.065 )0.865 and Tbo.135 (Feo.935 Bo.065 )0.865 are
shown in Fig. 6 and are representative of the other rare
earths investigated. Aside from minor d spacing and intensi-
ty variations the spectra are identical with that of the Nd
ingot (Fig. 5). Lanthanum does not form this compound,
presumably because its ionic radius is too large. The La alloy
consisted of elemental La and Fe in addition to a small
amount of an unidentified component which is presumably a
binary La-B or Fe-B phase.
Of the glass-forming elements we investigated, boron
appears unique in its ability to stabilize the phase of interest,
at least with Fe. Homogenized Ndo.135 (Feo.935 Me o.o65 )0.865
ingots with Me = Si, C, AI, Ge, and P consisted primarily of
Nd 2 Fe 17 • Since that intermetallic compound has a Curie
temperature of ~ 330 K, the fact that no significant coerci-
vity was observed in samples melt spun from those ingots is
not surprising.

MICROSTRUCTURE
As the x-ray work intimates, the kinetics of the rapid
solidification afforded by melt spinning are such as to foster
the formation of a fine-grained microstructure of the equilib-
rium R-Fe-B phase. Electron microscopy provides more ex-
plicit information. Figures 7-9 show scanning electron mi- FIG. 8. SEM micrographs of regions near the free surface (top), middle, and
crographs (SEM) of ribbon fracture surfaces from three of quench surface of a Ndo.135 (Feo.945 B O.055 )0.865 ribbon melt spun at v, = 14
the Nd o 135 (Feo.945 Bo.055 )0865 alloys (cf. Figs. 1 and 2). The m/s.

2080 J. Appl. Phys., Vol. 55, No.6, 15 March 1984 Croat eta/. 2080
 10

NdO.13 (FeO.95 BO.05)0.87

295 K after 450 K

·15 ·10 ·5 o 5
H(kOe)

FIG. 10. Demagnetization curves of a Nd ol3 (Feo95 B005 )087 alloy at several
temperatures T.

(BH)max of this sample at room temperature was 13.9

FI G. 9. SEM micrographs of regions near the free surface (top), middle, and
quench surface of a Nd ol35 (FeD 945 Bo .D" )0.865 ribbon melt spun at v, = 35
m/s.
ribbons fracture at grain boundaries, revealing the micro-
scopic texture. Each of Figs. 7-9 consists of three micro-
graphs depicting the microstructure near the free surface, in
the middle region, and near the quench (or wheel) surface.
The ribbons are 35-40,um thick (and -1.5 mm wide), so that
the area shown represents only a small fraction of the total.
The Us = 19 mls alloy (Fig. 7) is comprised of a surprisingly
uniform distribution of roughly spherical particles whose
diameters range from 20-S0 nm. Thinned foils examined in
transmission (TEM) exhibit the same general texture, al-
though the average particle size is somewhat smaller ( < 50
MGOe. As a consequence of the field dependence mentioned
previously, it was necessary to remagnetize the specimen in
the - 45 kOe pulsed field after demagnetization at each tem-
perature. Although a small irreversible loss occurred on first
returning the sample to room temperature, no additional
loss was noted after several subsequent cycles to 450 K. Over
the 295 K,;;;;T.;;;450 K intervalHci obeys an exponential rela-
tionship of the form HCi (T) = A exp ( - aT); a plot ofln Hci
vs T is presented in Fig. 11 (a). The reversible decrease in Hci
between 300 and 400 K is approximately - O.4%/K, a val-
ue comparable to that ofmischmetal-samarium cobalt mag-
nets 8 and very near the - 0.34%/K value for SmCos mate-
rials. 9
An issue of greater concern is the reduction in Br at
elevated temperatures, which results in a fairly large reversi-
(a)
9.5

nm). From this we surmise that some of the larger grains '0
:I:
observed by SEM are actually clusters of several crystallites.
Jl
As Fig. Sshows, theunderquenched(u s = 14m/s) alloy
consists of 20-S0 nm particles near the quench surface but 8.5
has a much coarser texture near the free surface. In contrast,
the microstructure of most of the rapidly quenched (us ;;;.30
m/s) alloys is glassy through the entire ribbon thickness. (b)
Several of these ribbons, however, did feature miniscule 5' 3.5
crystallites near the free surface. An example of this behav- :
ior is shown in Fig. 9; the magnification is 147 k X, roughly II
:I:
three times that in Figs. 7 and S. The minute crystallites '-.
CD
likely account for the small peaks in the x-ray diffraction co 2.5 NdO.13 (FeO.95 80.05)0.87
pattern for this sample [Fig. 5(d)].

300 350 400 450

TEMPERATURE DEPENDENCE OF Ho AND Br
T(K)
Demagnetization curves of a Ndo.13 (Fe O.95 BO.05 )0.87 al- FIG. 11. (a) In He; vs T for the alloy of Fig. 10. (b) B (at the point for which
loy at several temperatures T are displayed in Fig. 10; B/H = - 1) vs T for the same alloy.

2081 J. Appl. Phys., Vol. 55, No.6, 15 March 1984 Croat et al. 2081
ble temperature coefficient. A graph of D vs T for the
Ndo.13 (FeO.95 BO.05 )0.87 composition is shown in Fig. II(b).
The coefficient, defined as the decrease in magnetic induc-
tionDwith temperatureatD /H = - 1, is about - 0.15%/
K. This value is roughly three times that reported for rare
earth-cobalt-based magnets 9 but is less than that for oriented
ceramic magnets. The Dr reduction with temperature is re-
lated to the low ordering temperature, Tc ~ 560 K; Tc ex-
ceeds 900 K for Sm-Co materials. 9
SUMMARY
Our research demonstrates that small additions of bo-
ron ( < 6 at. %) dramatically improve the coercivity and en-
ergy product of melt-spun Nd-Fe and Pr-Fe alloys. Two es-
sential elements are involved. First, boron addition leads to
the formation of a new equilibrium R-Fe-B compound hav-
ing a tetragonal crystal structure. This compound forms
with many rare earths, but the Pr and Nd materials show the
best hard magnetic properties. Second, the melt-spinning
technique produces a fine crystalline microstructure of this
phase, whose characteristic particle dimension can be
changed by varying the quench rate. It is our present opinion
that the optimum properties are associated with the forma-
tion of single-domain particles. Using the observed Tc and
2082 J. Appl. Phys., Vol. 55, No.6, 15 March 1984
estimates of the anisotropy and exchange energies we obtain
an estimate of 80-160 nm for the single-domain particle di-
ameter; grain sizes measured directly by SEM and TEM on
the optimum samples are within or below this range.
ACKNOWLEDGMENTS
The technical assistance ofE. A. Alson, D. M. Kaufeld,
N. A. Schaffel, and T. H. VanSteenkiste is greatly appreciat-
ed, as is the enthusiastic support of F. E. Jamerson, J. C.
Tracy, A. D. Gara, andJ. R. Smith. Weare also grateful toJ.
L. Johnson, T. P. Schreiber, and A. M. Wims for the spectro-
scopic results.
I J. J. Croat, App!. Phys. Lett. 37, 109611980).
"N. C. Koon and B. N. Das, App!. Phys. Lett. 39, 84011981); N. C. Koon, C.
M. Williams, and B. N. Das, J. App!. Phys. 52, 2535 II 981).
'J.1. Croat, App!. Phys. Lett. 39, 35711981); J. App!. Phys. 53, 3161 II <JS2).
4J. J. Croat and J. F. Herbst, J. App!. Phys. 53, 2404 (1982).
'B. N. Das and N. C. Koon, Metall. Trans. A 14, 953 (1983).
"G. C. Hadjipanayis, R. C. Hazelton, K. Lawless, and D. J. Sellmyer, IEEE
Trans. Magn. (to be published).
7J. J. Croat, J. F. Herbst, R. W. Lee, and R. E. Pinkerton. App!. Phys. Lett.
(to be published).
"R. W. Lee, J. App!. Phys. 50, 2337 119791.
"H. F. Mildrum and D. J. Iden, Cobalt 35, 54119751.
Croat et a/. 2082