Volume 2, number SA

June 1984

MATERIALS LETTERS

THEMETALLURGYOFTHEIRON-NEODYMIUM-BORONPERMANENTMAGNETSYSTEM
H.H. STADELMAIER, N.A. ELMASRY, N.C. LIU and S.F. CHENG
Department of MaterialsEngineering, North olrolina State University,Raleigh, NC 276957907,

USA

Received 18 May 1984

The phdses coexisting with the magnetic boride Fel,Nd2E at 298 K are a-Fe, Fe17Nd2, Fe+NdB4, and
a-Nd. Metastable e-Nd and a modification of the magnetic boride are suggested by electron diffraction patterns. No Fe2Nd was found. The interaction between the magnetic boride and the Nd-rich liquid during sintering and/or heat treating is complex. It breaks up particles and introduces inclusions and is responsible for the unique properties of the sintered magnets. The liquid solidifies
into a eutectic whose presence causes serious degradation in a corrosive environment. The variation
of the microhardness of the magnetic boride with alloy composition and heat treatment is discussed.

1. INTRODUCTION
The recent announcement of a commercially
available permanent magnet based on Fe-Nd-B (1)
has raised questions about the mechanism responsible for the high coercivity. Magnets derived
from rapidly solidified ribbons (2),(3),(4),(5)
can be understood as small-particle magnets, but
sintered alloys said to possess a particle size
of 15 Pm (1) cannot. The ability of bulk alloys
of related Fe-Pr-B to increase their coercivity
by heat treatment (6) suggests that metallurgic
cal factors contribute to the success of Fe-Nd-8
as a permanent magnet. Detailed studies of the
three-component systems Fe-Nd-B and Fe-Pr-B are
in progress in our laboratory. In view of the
wide spread interest in the subject, we are releasing the following information that can be
considered established at the present time.

2. EXPERIMENTAL
The alloys consisting of l-2 g buttons of
Fe-Nd-B and, in one case, Fe-Cc-B were arcmelted under high-purity argon. They were annealed in evacuated (-10m2 Pa) and sealed capsules of fused silica for times and at temperatures stated in the text. Purities of the materials were, in mass %, electrolytic Fe 99.9,
Nd 99.9, Ce 99.9, boron 99.4. For the X-ray
diffraction analysis, 57.3 mm diameter powder
cameras with filtered CrK radiation were used,
Electron diffraction patterns were obtained on
a Hitachi 800 electron microscope. The microhardness was measured with a standard diamond
pyramid indenter and a force of 98 mN (10 g
load). Magnetic domain patterns were observed
using the magneto-optical
Kerr effect on sur0 167-557x/84/$

(North-Hollal~d

03.00 0 Elsevier Science Publishers B.V.

Physics Publishing Division)

faces polished carefully to remove traces of

cold work. Metallographic specimens were etched
in a solution of 5% HNOsin ethyl alcohol (Nital)
which was swabbed on.

3. ALLOY CONSTITUTION
3.1. Nomenclature
Names of the Fe modifications a,~,6 follow
standard notation. For the tetragonal magnetic
phase, variously referred to as Fe16Nd3B (7),
Fel,Nd2B (5), or Fe21NdsB (6), the symbol $
will be used for short.
3.2. Phase equilibria

at 9OOoC

From the isothermal section in progress it

follows that the region bounded by Fe, FeB, and
Nd is adequate to characterize the ternary phase
4. Phases observed at 900C are T-Fe, Fe17Nd2,
Nd-rich liquid, ternary Fe,+NdB*, and ternary $.
Binary Fe2.Nd, reported by Kuz'ma et al. (7), is
not found. For the higher boron phase the composition Fe4NdB4 is accepted because it is well
established in Co-rare
earth borides (8). The
powder Pattern of Fe,,NdBL is comoatible with the
lattice.constants
(tetragonal, a'= 0.709, c = 2.742
nm) reported bv Chaban et al. (7). At 900C m
cokxists with the phases listed above but not
with binary Fe borides, Phases that coexist with
$ at room temperature are a-Fe, Fe17Nd2, cc-Nd,
and FebNdB4. Only a-Fe and Fel7Ndz have permanent magnetic moments at 298 K.
3.3. Solidification
The ternary

boride 0 crystallizes

from the

411

June 1984

MATERIALS LElTERS

Volume 2, number SA

Fig.1. Fel,+Nd,B, as cast, etched with Nital,

100x.
Dendrites are 6, black areas are Ndrich eutectic.
Fe
melt (l),(5),(6). It does not, however, melt congruently, though we once believed that it did.
At the composition Fe @Nd2B, which is suggested
by the structure (9),[10), the primary crystallization product is d-Fe; the microstructure
is shown in Fig. 1. Annealing at 1200C causes
$ to recrystallize into much larger grains. It
also causes the amount of Fe, which is now y,
to decrease by coalescence into fewer particles,
see Fig.2. The alloy is not single-phase at this
A partial phase diagram of Fe-Nd-B
temperature.
is shown in Fig.3. The assumed invariant reactions in this region are marked l-4 in Fig.3
and consist of 1
-f Y-Fe + Fe,+NdB4
L
.
+ $
2 & 3. [L) + &-Fe + y-Fe + (0)
4.
+ Y-Fe -+ Fe17Nd.z + $
Reactions 2 and 3 are limiting cases in which the
amounts of L and $ do not change while 6 is transforming to y. Melting of + by the univariant reaction $J+ L + 6 along curve 2-3 occurs above the
6 + y transformation temperature. Therefore the

10

melting temperature of 0 is 214OOOC. The thin

lines in Fig.3 represent two-phase equilibria in
a low-temperature
isothermal section. Their meaning is obviously that the phases which they join
are in equilibrium. The lowest line emanating
from Fe2B terminates in binary NdB,+, following
Chaban et al. (7). In connection with Fig.3 the
following observations can be made and are significant to magnet fabrication: Solidification
of alloys containing >12 at.% Nd always ends
with a eutectic of which one component is elemental Nd. The melt is never exhausted before
it reaches the final eutectic composition at
about 70 at.% Nd. At -6 at.% B, alloys with >12
at.% Nd are certain to have an Nd-rich liquid
coexisting with $ at the sintering temperature,
see section 4.1 below. For Nd contents of 15
at.% or more (suggested for magnets), alloys
having <6 at.% B show $ with Nd+Fe
in the ascast structure. Those having >6 at.% B show 0
with Fe,,NdB,+but no Fe.

OF THE TETRAGONAL

4.1. Interaction

412

lh,

1200C,

water quenched,

FeB
AT.%

Fig.3. Ternary system Fe-Nd-B, projection of

liquidus surface and isothermal section at
600 C .

4. PROPERTIES

Fig.2. Fe14Nd2B,
Nital, 600x .

20
BORON,

BORIDE 4

of + with Nd-rich liquid

Binary Fe-Nd has a wide two-phase field of

Nd-rich liauid+FelTNdg.
which narrows with increasing temperature. An alloy located in that
field will contain increasing amounts of liquid
as the temperature is raised. A similar field
of L+$ or L+$+FebNdBb
exists in the ternary
so that the compacted magnet material must melt
partially during sintering. When an ingot is
remelted partially in this way, the liquid

Volume 2, number 5A

June 1984

MATERIALS LETTERS

Fig.4. Fe14Nd2B, lh , 1200C,

water quenched,
Nital, 300x.
Nd-rich liquid solidified in
cracks.

Fig.6. Magnetic domain pattern in Fe72.5Nd17.5B1a

308h,
900C,
unetched, polarized light, 250x .
Black areas are Nd-rich eutectic.

phase is nucleated at the grain boundaries. In

powders the liquid forms on the particle surface and can also be nucleated at internal defects that are generated during milling. At the
sintering temperature all particles are surrounded by the liquid. This inhibits recrystallization into large grains, a mechanism already
suspected by Sagawa et al. (1). It can, in fact,
be shown by mild etching with Nital that the
15 urn particle size reported by Sagawa et al.
(1) is virtual and that the true size is that
of the milled particles, or less. An example of
internal nucleation of the liquid in a largegrained alloy is shown in Fig.4, where the liquid fills the crack structure formed by thermal
shock. A substructure containing Nd-rich liquid
can be observed in as-cast specimens: The outer
portion of the $ crystals appears broken into
blocks floating in the liquid, Fig.5. This structure has the wrong morphology and is also too
$-rich to be the eutectic itself and is probably
caused by remelting during the original solidification. It could form when a metastable eutec-

tic is converted to a stable one. In support of

this suggestion we can point to similar structures in Fe17Ndz and Fe4NdB4, both of which also
interact with the Nd-rich liquid.

Fig.5. Fe77.sNd1sB7 s, as cast, Nital, 950x.

Substructure at liq;id/$ interface.

4.2. Crystal

habit of $I

This phase crystallizes from the melt in

platelet form, with rapid growth along the basal
plane. When dendrites of Fe are primary, this
growth is inhibited, and the grain shape is
more nearly equi-axed. Thermally demagnetized
grains have domain patterns with boundaries parallel to the crystallographic c-axis (easy magnetization), see Fig.6. Sections normal to the caxis show a maze type domain pattern. At the interface between $ and the Nd-rich eutectic, a
ledge structure can be observed in unetched specimens, see Fig.7. It is visible.because a portion
of the soft eutectic gets washed out during polishing, revealing the steps as fringes. They go
out of focus as their elevation drops. The phenomenon is observed only when the basal plane,

Fig.7. Ledge structure at interface between 0

and Nd-rich eutectic in Fe,,Nd,,B,,, as cast,
unetched, 950x
413

Volume 2, number SA

recognizable by its maze domain pattern, is parallel to the specimen surface. These are qrowth
steps in the basal plane. The step height-is
typically 0.1-0.2
urn, and the steps are likely
to continue into the crystal as planar defects.

4.3.

Plastic deformation,

microhardness

The usually brittle $ is capable of deforming

plastically, as seen in the microstructure when
grain boundaries can be literally dragged along
by scratches. Plasticity is also evidenced by
zigzag domain boundaries, observed when pre-polish grinding was uni-directional.
Resistance to
plastic deformation can be measured by microhardness which varies with alloy composition and
history, Table 1. At constant Nd, the hardness
increases with B content. This may be a proxim-

Table 1. Microhardness

of Fe-Nd-B alloys.

Composition,
at.%
Fe
Nd
B

TreatDiamond pyramid hardfnnnt,t;*) ness, 10 g load**)

a
a+$
$

85

AC
300/900

12.5

2.5

I97(16)
486(83)

80

17.5

2.5

AC

360(23)

2526273

90

300/900

434(35)

268(35)

85

10

AC
300/900

534(78) 269(58)
502(50) 277(O)

82.5 12.5

300/900

473(32)

82.3 11.8

5.9

AC
l/1200

46!i;[Z#

300/900

664(69)

~~0,900
300/900
300/600

~~~~~~~
614(53)
493(25)

300/900

640(40)

i$;;r;'"l

776(76)

300/900

504(50f

72.5 12.5 15

300/900

763(70)

70

AC

782(79)

82.5 10

7.5

80

7.5

12.5

77.5 15

7.5

77

15

75

17.5

7.5

15

15

Fe,NdB,+

ity effect, the hardness being influenced by the

hardness and closeness of a neighboring phase.
At constant B the variation with Nd content is
not dramatic. High coercivity sintered alloys
have moderate values of microhardness (in the
400's). This may also not be inherent but due to
the ubiquity of the soft eutectic (see section
4.1). The inherent hardness of 0 (>600) is comparable to that of hardened steel.
4.4. Crystal structure
Powder X-ray diffraction patterns reveal
little information that could explain the hardness variations. Line shifts suggesting compositional changes of $Iare absent, the lattice constants remain a=0.880.
c=1.218
nm in all alloys. Intensity variations are observed but not
easily assessed (structural? preferred orientation?). Line broadening of the type l/case
(small particles) is observed in powders and
sintered specimens. In electron diffraction patterns some Q, crystallites had reciprocal lattice
rows (hhn) for which reflections with I?=Zn+l
were weak; in other crystallites they were absent. From this limited information it is not
certain whether the structure is a derivative
of $, subject to the condition (hh&): R= Zn,
or whether all ilare even, so that c is halved.
A powder diffraction pattern satisfying the
latter condition was observed in an alloy
Fele,CesB held 24 h at 900OC,but
never in FeNd-8. IF a phase with c' =$c
exists in Fe-Nd-B
it is not discernible in an x-ray diffraction
pattern. Coexisting regions with c and fit
would be accompanied by a defect structure.

5. THE Nd-RICH

93(15)

96(2)

Nd-eutectic

72.5 12.5 15

300/900

1334(68)

70

10

20

300/900

715(115)

20

80

300/500

46(2)

25

70

300/600

73(8)

30

60

10

300/600

61f16)

*) As cast. **) Numbers

in paren. = std.deviation.

414

June 1984

MATERIALS LETTERS

EUTECTIC

The overall composition of the eutectic

constituent found in magnet alloys is 70 at.%
Nd with little boron. Its X-ray tiiffraction
pattern is consistently that of "double" hexagonal a-Nd. A region in a sintered magnet that
was imaged as a grainy microconstituent
located
between crystallites of $ showed an electron
diffraction pattern consisting of Debye rings.
it was indexed as body-centered cubic, a=
0.370 nm. The microstructure and diffraction
pattern identifies it as eutectic B-Nd containina considerable dissolved Fe. The (110)
or (206) reflection of this ring pattern is'
sometimes seen superimposed on the single
crystal pattern of +, emphasizing the pervasiveness of the Nd-rich liquid.

6. CORROSION
It was mentioned earlier (6) that Fe-Pr-B
alloys could corrode to the point of complete
pulverization. Fe-Nd-B alloys also tend to corrode catastrophically under some conditions, as
seen in metallographic
specimens from which the

Volume 2, number 5A

MATERIALS LElTERS

was incompletely
removed. This behavior
is not surprisitlg in view of the ever present
Nd-rich eutectic which apparently has a large
electrochemical potential difference against 0.
The implications for magnets exposed to a corrosive environment are obvious.
etchant

June 1984

ACKNOWLEDGEMENT
This work was supported
of Naval Research.

by the US Office

REFERENCES
7. HIGH COERCIVITY

IN SINTERED

MAGNETS

The function of the Nd-rich liquid as a sintering aid was discussed by Sagawa et al. (1).
The import-ice of the liquid phase is seen by
extrapolatinq their curve of H, vs. Nd content
which.goes to zero at 12 at.% Nd. Thus, without
the Nd-rich liauid. which is not found below
12 at.% Nd (section 3.3), the coercivity remains
negligible. The thought that the liquid somehow
conditions the particle surface to inhibit domain nucleation (1) is not realistic, unless by
that we mean further breaking up of particles
under the circumstances described in section
4.1. Apparently the non-trivial effect of particle size on H, introduced by milling is not
lost in sintering but further enhanced by the
action of the Nd-rich liquid. We believe that
a imajor contribution to coercivity in sintered
Fe-Nd-6 magnets is due to particle size and a
smaller fraction to inclusions or a defect
structure. The success of the sintered magnet
system must be attributed to a favorable alloy
constitution, which includes the absence of
phases between the magnetic boride and the Ndrich eutectic. If present, they would interfere with the interaction between boride and
liquid.

(1)

M. Saqawa, S. Fujimura, N. Toaawa, H. Yamamote,-and Y. Matsuura,.J. Appi. Phys. -55

(1984) 2083.

(2)

N.C. Koon and B.N. Das, J. Appl. Phys. -55

(1984) 2063.

(3)

J. J. Becker, J. Appl. Phys. -55 (1984) 2067.

(4) G.C. Hadjipanayis, R.C. Hazelton,

Lawless, J. Appl. Phys. -55 (1984)

and K.R,

2073.

Herbst, R.W. Lee, and F.E.

Pinkerton, J. Appl. Phys. -55 (1984) 2078.
(6) H.H. Stadelmaier, N.A. EeMasry, and S. Cheng,
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(5) J.

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(7) N.F. Chaban, Yu.B. Kuz'ma, N.S. Bilonizhko.

0.0. Kachmar, and N.U. Petrov, Dopov. Akad:
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Met. -67 (1979) 51.
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W.B. Yelon, Phys. Rev. B, in press.
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and

and R. Fru-

415