Study of magnetic properties and Mössbauer effect of PrFe and meltspun PrFeB alloys

L. R. K. Rotenberg, R. F. Oliveira, H. R. Rechenberg, and F. P. Missell

Citation: Journal of Applied Physics 57, 4127 (1985); doi: 10.1063/1.334640

View online: http://dx.doi.org/10.1063/1.334640
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 Study of magnetic properties and Mc;ssbauer effect of Pr-fe and me~t-spun
Pr-fe-B anoys .
L. R. K. Rotenberg, R. F. Oliveira, H. R. Rechenberg, and F. P. Missel!
Instituto de Flsica, Universidade de Siio Paulo, c.P. 20516, 01498 Siio Paulo, S.P., Brazil

We prepared samples of the intermetallic compound Pr2 Fe 17 that were free of segregated Fe and
measured the Mossbauer spectra as a function of temperature, obtaining T c = 301 ± 2 K.
Mossbauer spectra from samples of annealed Pr2 F<14 B powder show considerable complexity.
Melt-spun ribbons of Prls F~9 B6 , magnetized to 20 kOe, showed an intrinsic coercive field
Rei = 14.5 kOe at room temperature. Mossbauer spectra of melt-spun material show slight
differences with respect to those from annealed ingots. The origin of these differences is not yet
clear.

INTRODUCTlON Pr2 Fe 17 phase, we often observed segregation of a-Fe upon

The announcc~ment of a commercially available perm a-
nent magnet based on a phase of the Nd-Fe-Bsystem l has led
to an acute interest in the magnetic properties of these ter-
nary compounds. Although the magnetic material reported
in Ref. 1 was obtained by powder metallurgy techniques,
other workers 2- S have observed high intrinsic coercivities
Rei in melt-spun ribbons. There is now general agreement
that the ternary magnetic phase has a complex tetragonal
structure and composition Nd 2 Fe14 B. 1.~9 The correspond-
ing Pr-Fe-B compound has been reported s to possess an even
higher Hd but a somewhat lower remanence. Recently, Pin-
kerton and Dunham lo presented Mossbauer measurements
on a boron-free Ndo.lS Feo.85 alloy and on a Nd-Fe-B alloy
containing a few atomic percent of boron. In the latter case,
the MOssbauer spectrum was reported to be considerably
less complex than in the former. In the present work, we
present Mossbauer spectra for Pr2 Fe 17 and for two samples
containing boron, powdered Pr 2 Fe I4 B, and melt-spun rib-
bons of composition Prls Fe'9 B6 . Magnetization measure-
ments for the melt-spun ribbon are also presented.
SAMPLIEPREPARATION
The samples used in this work were made by combining
the elements Fe (99.98% pure), B (99.8%), and Pr (99.9%) in
an arc furnace under an argon atmosphere. In preparing the
starting with the stoichiometrically correct proportion of Pr
and Fe. The segregation was evident in both the Mossbauer
spectra and in the x-ray powder patterns, and is that referred
to by 10bhson et al. 11 as the cause for the early confusion
about the composition of this phase. This difficulty was re-
solved by beginning with a slightly Pr-rich composition (Pr
Fe, ). After arc-melting, a Pr-rich surface layer was removed
with nitric acid and the remaining material was then an-
nealed at 800·C under a vacuum of 10- 6 Torr for 65 h. The
resulting material showed the Pr2 Fel7 powder pattern 12
without a trace of segregated Fe. The purity of the phase is
also evident from the Mossbauer spectra presented below in
Fig. 3.
An ingot of Pr2 Fe l4 B was prepared in the arc furnace
and then homogenized at 800 ·C for 33 h under a vacuum of
3 X 10- 6 Torr. The powder pattern, obtained with Cu Kcx
radiation, is shown in Fig. 1. With the exception of a weak
line at 28 = 44.7 due toa-JFe, this spectrum agrees wen with
those presented by Croat et al. 5 and Sagawa et al. 1 for the
Nd-Fe-B alloys.
Alloys for melt-spinning were prepared with the com-
position PrISFe'9B6' since the corresponding Nd alloy
8 P~5 F~ 86
T=300K
ribbon
z 4
o
~
N
~ 0r---~-----4~~------~
w
§
~ -4

-20 -10 0 '() 20

APPLIED MAGNETIC FIELD( kOe)
FIG. 1. Intensity of diffracted eu Ka radiation vs angle 28 for Pr2 Fel.B FIG. 2. Magnetization vs applied magnetic field for a melt-spun ribbon of
powder. Pr,s Fe7 • B. at T= 300K. Note that 8 = H +M.

4127 J. Appl. Phys. 57 (1), 15 April 1985 0021-8979/85/014127-03$02.40 @ 1985 American Institute of Physics 4127
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 low value of the energy product. On the other hand, the
!", .-'. ./,. ,-. ..
.-."... ~~: eo: ""'.,/" '., :. . ..f "0,_• asymmetry of the hysteresis loop suggests that the 20-kOe
. ........ 0. ~; ..
.,,; .... external field was not large enough to saturate the ribbon.
Thus, higher magnetizing fields would probably improve the
§ 78K values obtained for Hei ,Brand (BH )mlU .
.D
o ..- '"
<1\
§
....... - ............ ,.,. 1f"I'i'8. \IIIIW -
MOSSBAUER SPECTROSCOPY
57 Fe Mossbauer spectra of the Pr 2Fe 17 phase are shown
o
U
...' 296K
in Fig. 3. The Curie temperature of this sample, as deter-
'. . mined by the coUapse of the magnetic hyperfine structure,
I I I I was Tc = 301 ± 2 K, higher than the value reported by
-3 0 3 6
mm/sec Strnat,14 Tc = 283 K. The spectrum at 78 K is very similar
to those reported by Levinson et al. IS and by Gubbens et al. 16
FIG. 3. Mossbauer spectra of the intermetallic compound Pr2Fe 17 at tem- except that the samples studied in Refs. 15 and 16 contained
perature indicated. a-Fe as wen as the Pr2 Fe l7 intermetallic phase. In our sam-
ples containing a-Fe in addition to the Pr2 Fe 17 phase (typi-
cally 15% of the total spectral area), Curie temperatures
showed the highest values of H ei • 13 The ribbons were ob- were enhanced, varying from 315 to 323 K.
tained by spinning in air onto a copper wheel rotating with a Room-temperature Mossbauer spectra of (a) powdered
surface speed - 17 m/sec. The ribbons so obtained were very Pr 2 Fe l4 B and (b) melt-spun ribbons of PrlSFe79B6 are
slightly oxidized on the outer surface. The x-ray diffraction shown in Fig. 4. A small contribution from a-Fe can be no-
pattern for the ribbon showed the same lines as in Fig. 1, with ticed in both spectra. The great similarity between these
a slight broadening and reduction in intensity, as would be spectra indicates that the ternary phase formed is most prob-
expected for small grains. ably the same, despite the differences in sample composition
and preparation. We do not observe a simplification of the
MAGNETIZATION Mossbauer spectrum in the boron containing material as was
Magnetization measurements were made with a vibrat- reported for the Nd-Fe-B alloys. to The most obvious differ-
ing sample magnetometer at room temperature. An exam- ences between the spectra is the greater relative intensity of
ple, for a Prl5Fe79B6 ribbon, is shown in Fig. 2. (Note that lines 2 and 5 of spectrum (b) in comparison to those of spec-
we are using rationalized cgs units where B = H + M. To trum (a). This might seem to be a consequence of preferential
obtain the magnetization in Gauss we used a density d = 7.6 orientation of Fe magnetic moments parallel to the ribbon
g/cm 3 , appropriate for a Nd-Fe-B alloy.6) The ribbon of Fig. plane. However, this ribbon was transformed into powder
2 was magnetized to 20 kOe from the virgin state and then M and the resulting MOssbauer spectrum also presented a
was recorded. In the present case we find Hei = 14.5 kOe, greater relative intensity for lines 2 and 5, similar to spec-
with a remanence Br = 5.8 kG and an energy product trum (b) of Fig. 4. Spectra at 78 K (not shown) are very simi-
(BH )max = 4.2 MG Oe. The low remanence and the unfavor- lar to those at 296 K, with effective fieJ.ds only 15% greater,
able second quadrant demagnetization curve account for the indicating aTe much higher than room temperature.
The observed complexity of the Mossbauer spectra is to
be expected, since neutron 6 and x-ray 7 diffraction data on

-. a-Fe
Nd2 Fe14 B reveal a complex crystallographic structure. Due
to the similarity of the powder patterns of the Nd and Pr
.- .. :.,".,
a
'.
.', .'.,
." '- C()tttpounds, we expect the Pr-Fe-B com.pound to also pos-
se~t, six inequivalent Fe sites. We are in th.e process ()ffitting
OUt spectra to determine the hyperfine parameters corre-
.'
.: sponding to those sites. These fits will help to decide whether
the differences observed in Fig. 4 are due to the slight compo-
-6 -3 o 3 6
mm/sec
sition differences or to the microstructure induced by mel.t
a-Fe spinning.

".
,
.... .-/ .1"'"" •
~
•J"..
.. CONCLUSIONS
"
..0 • ~ ,
....
~ b .: We prepared samples oO?r2 Fe 17 that were free of segre-

]~I~I__'_'_~__~-______~I______\~____; __-LI_ gated Fe, using a slightly Pr-rich starting composition. T c

~ ~
FIG. 4. MOssoouer spectra at room temperature of (a) annealed Pr2 Fe" B
powder and (bl melt-spun Pr I~ Fe19 B. ribbon. The a-Fe lines are indicated
above each spectrum.
was obtained from M6ssbauer measurements as a function
0 3 6 of temperature and was found to be lowest (301 ± 2 Kl in a
mm/sec
sample free of segregated Fe. Samples of powdered
Pr2Fel4B and melt-spun ribbons of PrlsFe79B6 showed
complex Mossbauer spectra as might be expected from a
compound possessing six inequivalent Fe sites. M6ssbauer

4128 J. Appl. Phys., Vol. 57, No.1, 15 April 1985 Rotenberg et a/. 4128
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 spectra from an annealed ingot and a melt-spun ribbon seem 6J. F. Herbst, J. J. Croat, F. E. Pinkerton, and W. B. Yelon, Phys. Rev. B
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4129 J. Appl. Phys., Vol. 57, No.1, 15 April 1985 Rotenberg et al. 4129
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