Formation and properties of NdFeB prepared by mechanical alloying and solidstate

reaction
L. Schultz, J. Wecker, and E. Hellstern

Citation: Journal of Applied Physics 61, 3583 (1987); doi: 10.1063/1.338708

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 Formation and properties of NdfeB prepared by mechanical aUoying and
soHd ..state reaction
l. Schultz, Jo Wecker, and E. Helistern
Siemens AG, Research Laboratories, Erlangen, West Germany

Magnetically isotropic NdI5Fe77B~ powder is prepared by mechanical alloying and a solid-state

reaction from the elemental powders. Due to the extremely short reaction time (for example,
10 min at 700 °C) the magnetically isotropic particles have a very fine microstructure
comparable to rapidly quenched samples, show a pinning-type behavior and possess excellent
magnetic values such as IRe up to 13 kOe and Bllmax up to 12.8 MGDe. Details on the
development of the microstructure during milling, the reaction kinetics, and the magnetic
properties are reported.

INTRODUCTION The x-ray diffraction investigations are performed in a

Mechanical alloying! has caught a lot of interest since it
has been shown that by this technique a large number of
amorphous TM-TM alloys (TM represents transition met-
al) can be formed. 2 - 5 In this process, the elemental powders
are mixed together and milied for several hours in a high-
energy baH mill, In the early stage of the milling process the
elemental powder particles are welded together. Character-
istically layered particles are formed. 103 .4 Further milling re-
fines the microstructure more and more. Finally a true alloy-
ing by a solid-state reaction takes place if this reaction is
favored by a negative enthalpy of mixing as has been demon-
strated for the TM -Zr and TM -Ti alloy series with TM vary-
ing from eu to V.S In addition, an amorphous phase is
formed if the temperature where the solid-state reaction
takes place is well below the crystallization temperature of
this amorphous phase. In this case, glass formation seems to
be favored by a nucleation process. 6 Mechanical anoying of
boron-containing alloys has been studied for FeZrB. 7 Start-
ing from elemental Fe, Zr and amorphous B powders, mill-
ing produces amorphous FeZI' powder with finely dispersed
B particles, showing that elemental amorphous B is not me-
chanically alloyed. But an additional diffusion treatment Jets
Siemens D500 diffractometer using CuK" radiation (A
= 0.154 nm) and a solid-state Si (Li) detector. To avoid
oxidation the powder samples are covered under a Kapton
foil.
For the magnetic measurements, which are performed
in a vibrating sample magnetometer at 20 "C, the powder is
embedded in an epoxy resin after the heat treatment. The
hysteresis loops are measured after premagnetization in a
7.5-T pulsed field.
RESULTS
The baH mining first produces powder with a layered
microstructure of Fe and Nd, The submicron boron powder
remains undeformed. It is caught by the colliding Fe and Nd
particles which are cold welded and is, therefore, embedded
in the FeNd interfaces (or within the Fe or Nd layers if Fe-
Fe or Nd-Nd collisions occur). Figure 1 (a) shows this char-
acteristic microstructure after a 2-h milling time, Further
milling leads to a refinement of the layered microstructure
until the Fe and Nd layers are no more resolved by light
microscopy [seeFig.l(b)] (after a 30-h milling) The x-ray 0

the boron diffuse into the FeZI' and form amorphous FeZrB.
In this study we replaced Zr by Nd in order to investigate
whether amorphous or at least microcrystalline NdFeB can
be produced using this technique and whether this material
has the same potential with regard to the magnetic proper-
ties as rapidly quenched NdFeB which is known to be an
excellent hard magnetic material. 8
SAMPLE PREPARATION
For the experiments we used pure elemental powderso
The Fe powder si2'~ vari.es from 5 to 40 11m, the Nd particles
are smaller than 0.5 mm, and the size of the amorphous B is
iess than 1 pm. The powders are mixed to give an average
composition of Nd ls Fe77 B8 and are sealed under argon (less
than I-ppm O 2 and H 2 0) in a cylindrical steel container.
The milling is performed in a conventional planetary baH
mill without coolingo
diffraction pattern (Fig. 2) shows broadened intensity peaks
cfpure Fe, The Nd peaks are smeared out and, therefore, no
longer detectable. It is assumed, but still to be proved by
TEM, that the powder particles [Fig. 1 (b)] consist of very
fine Fe and Nd layers with the embedded boron particles.
There are no hints that either a crystalline or an amorphous
FeNd phase is formed during milling. Thermodynamic cal-
cuiations based on the Miedema mode1 9 show that for FeNd
the difference flG of the free enthalpies between the amor-
phous phase and the layered composite is positive, whereas
tJ..G for FeZr (Ref. 10) is negative over a wide concentration
range. Therefore, by mechanical alloying ofFe-Zr-B the for-
mation of an amorphous FeZr phase is expected (and ob-
served 7 ), but for Fe-Nd-B a layered Fe-Nd composite is en-
ergetically favored as it is similarly found for V -Zr or Cr-ZL 5
The formation of the crystalline Nd 2 Fe 17 phase seems to be
prevented by nucleation problems.

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Ie!
FIG. 1. (a) Microstructure of Nd-Fe-B powders after 2-h milling time. (b)
Microstructure of Nd-Fe-B powders after 30-h milling time. The boron par-
ticles are embedded in the Fe-Nd matrix. The individual Fe and Nd layers
are not resolved. (c) Microstructure of mechanically alloyed and solid-state
reacted Nd!sFenB g powder (30-h milling, 1 h at 600·C heat treatment).
In order to obtain the desired hard-magnetic Nd2 Fe 14B
phase, a solid-state or interdiffusion reaction is necessary.
Figure 1(c) shows a powder which has been milled for 30 h
and reacted for 1 h at 600 "C. The boron particles are com-
pletely dissolved in the FeNd powder. The x-ray pattern
(Fig. 2) clearly shows the intensity peaks of the Nd2 Fe l4 B
phase. The solid-state reaction kinetics have been studied in
detail by differential scanning calorimetry (DSC). Figure 3
shows the DSC traces (at l00-K/min heating rate) of me-
chanically alloyed NdFeB powder after increasing reaction
times at 600 0c. The step in heat flow beyond 300 ·C is relat-
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40 50 60 70
Scattering angle 29
FIG. 2. X-ray diffraction patterns ofNd-Fe-B powder (a) after 30-h milling
and (b) after 30-h millL'lg and 1 hat 6OO·C heat treatment.
ed to the Curie temperature Tc ofthe Nd2 Fe i4 B phase. The
unannealed sample does not show any irregularity at this
temperature. After 1 min at 6OO·C the Curie temperature
can be detected by the step in the DSC traces. With increas-
ing reaction time the step size reflecting the amount of
Nd2 Fe 14 B formed by solid-state reaction increases only up to
4 min and remains constant for longer annealing. T c in-
creases slightly up to about 20 min. It is concluded that most
of the interdiffusion reaction is finished within only 4 min at
600 °e. Further annealing seems to improve the atomic or-
der of the Nd2 Fe 14B phase monitored by the Tc change and
to coarsen the grain size which is detectable by measuring
the coercivity (see below). For a reaction temperature of
550 cC the interdiffusion reaction as indicated by the T c step
is finished after about 30 min and even at a temperature as
low as 500 ·C the reaction takes only several hours.
The coercivity is plotted in Fig. 4 as a function of reac-
tion time for different reaction temperatures. The unreacted
samples do not show any coercivity. The magnetic phase is
a-Fe. In the initial stage of the reaction the coercivity in-
creases very fast, later it passes a maximum and drops a little
bit for long-time annealing. The low-temperature reaction at
500 °C leads to a maximum after 10 h with a coercivity of
only 5 kOe. At higher temperatures the maximum is shifted,
as expected, to a much shorter reaction time (10 kOe after 1
~
.!S
l<
.=l
....
"-'
...""
L:
~
~
"-
OJ
.c;
.....
Q
><
l.U
200 250 300 350 400
Temperature (·C)
FIG. 3. DSC traces (100 K/min) of mechanically alloyed NdFeB powder
after increasing reaction times at 600 ·C. The size of the step in heat flow
beyond 300 ·C which is related to the Curie temperature is a measure for the
amount of Nd 2Fe,.B phase formed during the reaction.
3584
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14
12
~ 10
4 9 i6
Reaction tine (hj
FIG. 4. Coercivity of mechanically alloyed Nd15FenB. powder vs reaction
time for different reaction temperatures.
11 at 600 ·C and 13 kOe after 10 min at 700 ·C). With regard
to these data and the DSC data it is concluded that when the
reaction is mostly completed after very short reaction times
(compare Fig. 3) the grain size is stilI too small for maxi-
mum coercivity which is obtained only after grain coarsen-
ing. Overaging leads to a reduced coercivity. This is also
confirmed by a detailed minor loop analysis. For example, a
sample reacted for 1 hat 6OO·C ([He = 10 kOe) predomi-
nantly shows a pinning-type behavior whereas a sample
reacted for 1 hat 900 ·C exhibits a nucleation-type behavior.
CONCLUSIONS
These results show that by mechanical alloying and a
following solid-state reaction it is possible to prepare iso-
tropic N dFeB magnets with interesting magnetic properties.
The values of the best sample, so far, are (after 30 min at
700 ·C): Dr ;:::;0.8 T, BHmaK = 12.8 MGOe, and IHe
= 12.75 kOe with these data only being related to the mag-
netic powder neglecting the volume percentage of the bond-
ing resin. A further increase in coercivity seems to be possi-
ble by variation of composition and optimization of the
reaction conditions. This material shows a pinning-type be-
havior and seems to be comparable with isotropic rapidly
quenched material. I< In order to produce magnetically aniso-
tropic compacted material similar techniques as for rapidly
quenched materials l ! should be applicable.
With regard to the solid-state reaction the preparation
of NdFeB by mechanical alloying is related to the ternary
diffusion process by Stadelmaier et al., 12 where Fe, Nd, and
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Fe2B powders are compacted and then reacted at 700-
900 'C, However, the main advantage of the mechanical al-
loying process is that the dimensions of the elemental layers
in our samples are smaller by several orders of magnitude
and that the individual powder particle itself is a mixture of
the elements involved in the alloy. Furthermore, the use of
the pure elements and of the amorphous boron provides a
high driving force for the interdiffusion reaction. Therefore,
the reaction time is very short and similar to the annealing
time necessary to optimize overquenched samples,11 leading
to a pinning-type behavior. Longer reaction times as, for
example, 20 h at 700 'C, lead to grain coarsening and, as a
25 result, to a nucleation-type behavior as it has been demon-
strated by Hilscher et ai.13 for materials prepared by the
Stadelmaier process.
ACKNOWLEDGMENTS
The authors thank E Gaube and M. Greiner for techni-
cal assistance, D. Keilholz for x-ray diffraction analysis, and
K. W ohUeben and H. HiUsing for helpful discussions.
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Schultz, Wecker, and Helistem
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