Journal of the Less-Common Metals.

31 (1973) 21 l-220
N$, Elsevier Sequoia S.A., Lausanne - Printed in The Netherlands

CRYSTAL STRUCTURE

Y. KHAN
Iustitur far
(Received

211

OF SmCo,

and D. FELDMANN
WerksroJfe der Elektrorechnik der R&r-Unitlersitiit Bochum ( West Germany)
October

16, 1972)

SUMMARY

An alloy having the composition SmCo, has so far been considered to be a

single phase compound with the CaZns-type structure. It is shown by X-ray analysis
and other methods that this material is actually always obtained as a composite
of two phases, one having the CaZn,-structure and the other being a variant of that
structure with doubled lattice constants.

INTRODUCTION

In recent years, much interest has been taken in the RCo,(R=Y,

La, Ce,
Sm) alloys because of their magnetic properties which make them very favourable
from the permanent magnet viewpoint. All of the work on these alloys has been
based on the assumption that RCo, is invariably a single phase compound with the
CaZn,-structure.
In this paper preliminary results are reported of a structural
reinvestigation of SmCo, undertaken to determine whether it is in fact single phase.
Wernick and Geller have reported crystal structure data of most of the RCo,
alloys, except LaCo,, SmCo, and a few of the heavy RCo, compounds. Starting
from a very detailed structural investigation of the compound ErNi, which they
found to have the CaZn, structure, they assumed all the RCo, compounds to be
isotypes. Haszko investigated SmCo, and confirmed this assumption. Later,
LeMaire3, Buschow4, and Lihl et ah5 independently confirmed the results of
Haszko and reported the lattice parameters of materials at the Co-rich and
Sm-rich borders of the homogeneity region of SmCo,. None of these authors
presented a detailed comparison of the calculated and observed structure data of
SmCo,. Shibata6, in an investigation of the effect of heat-treatment, was the only
author to present X-ray diffractometer patterns of SmCo, powder. Apparently no
thorough structural investigation of SmCo, has been carried out, either on powder
or on single crystals.
EXPERIMENTAL

Alloys in the composition range SmCo,.,-SmCo,,,

were prepared. The Sm
and Co metals used were supplied by HEK, GmbH, Liibeck (Germany) and had
reported purities of 99.9 and 99.999 wt.%, respectively. A second series of alloys

212

Y. KHAN, D. FELDMANN

was prepared using Co and Sm of industrial purity, supplied by Th, Goldschmidt

AG, Essen (Germany). In order to avoid crucible contamination, alloys of 1-3 g were
melted with a tungsten electrode on a water-cooled copper hearth in an atmosphere
of highly-purified argon. Alloy buttons were crushed into several pieces and remelted
to obtain homogeneity. With this procedure weight losses were found to be virtually
negligible. Besides these alloys, three commercial samples with the approximate
composition SmCo,. 2 were investigated.
The as-cast buttons were homogenized for 30-120 h between 1000 and
1100C. Heat-treatments
of bulk and powder samples were performed in the
temperature range between 500 and 1300C in argon-filled quartz tubes with
tantalum foil linings.
Most of the X-ray measurements were made with an Enraf-Nonius Guinier
camera, Model II. In addition, a Philips horizontal goniometer with scintillation
counter for powder analysis and a Weissenberg camera (Enraf-Nonius) for single
crystals were used.
Chemical analyses were made with a Philips X-ray fluorescence diffractometer
and a Unicam atomic absorption spectrometer. The results were checked using
classical gravimetric methods.
RESULTS AND DISCUSSION

Of the 10 alloys, repeatedly prepared in the investigated composition range,

those close to the 1:5 stoichiometry were free from the known neighboring phases.
Figure 1 shows Guinier patterns of Sm-Co alloys, containing: (a) SmCo, and
Sm,Co,, (b) SmCo, and Sm$or,,
and (c) apparently single phase SmCo,.
The Guinier pattern of Fig. l(c) can super~cially be indexed as the hexagonal
CaZn,-type structure. After long exposure, however, three additional weak lines were
observed at 46=35.2, 41.3 and 48.8 (Fig. 2(b)). It would seem reasonable to
explain the existence of these three additional lines in terms of the presence of the
neighboring phases, Sm,Co, or Sm,Cor 7. However, a close examination of the
pattern in Fig. 1 and the overexposed photograph in Fig. Z(b) shows that these Iines
do not belong to any of these phases, as the strongest lines of either phase are
missing. The possibility that these lines are reflections due to the half wavelength
harmonic of the CoKa radiation has been excluded on the basis of corresponding
experiments on Si and CaCu,.

Fig. 1. Guinier X-ray photographs of SmCo,. (a) Two-phase with Sm,Co,, (b) two-phase with Sm,Co,,,
(c) apparently single phase.

This suggests that either (a) SmCo, is single phase with a structure other
than CaZn,, or (b) samples with SmCo, composition are two-phase, one phase
having the CaZn,-type structure and the other a yet unknown variant of this

213

Fig. 2. Guinier X-ray photographs of SmCo, for various exposures. (a) Calibration substance (Si +a little
SiO,), 14.0 h CoKa; (b) SmCo, +calibration substance, 14.0 h Co&; (c) SmCo, +calibration substance,
3.5 II Co&; (d) SmCo, +calibration substance, 1.0 h CoKa.

structure where the main diffraction lines coincide with those of the CaZn, structure.
In order to decide between these two possibilities, a series of etching
experiments were made and photomicrographs, with and without polarized light,
were taken. X-ray powder diffraction intensities of SmCo, (CaZn,-type) were
calculated and compared with those found experimentally (Table I).
Most of the polished samples of the homogen~ed SmCo, compound
TABLE I
SmCo, (CaZns-TYPE) STRUCTURAL

DATA

Experiment: SmCo, (alloy annealed at 1000C for 72 h; powder 14 h 55OC/wa)

Guinier-photograph 4 h CoKa, calibrated with Si.
Structure:
CaZn, Typea = 4.99,
c = 3.97,
c/a = 0.795,,.
Atom-parameters were taken from CaZn, (Haucke4).
Remarks:
I&,,~,CIlo- HPLGIFJ*
Where H is the multiplicity of the reflex, PLG is calculated for Guinier Camera Mode&II,
Enraf-Nonius, Hotland, after K. Sagel.
All reflexes permitted by the space group are included.
_~_..
Iohs.
(h k 1)
leolc.
sin 6corc. sin &
^
0.0428
38
w
100
0.0428
0.0506
143
mw
001
0.0506
0.0934
1256
st
101
0.0934
0.1284
849
m+
110
0.1283
0.1712
990
mst
200
0.1711
0.1789
2799
VSt
Ill
0.1789
0.2026
742
m
002
0.2025
0.2218
153
mw
201
0.2237
0.2455
18
VVW
102
0.2453
0.2995
15
ww
210
0.2994
0.3309
554
m112
0.3308
0.3500
543
m211
0.3500
0.3737
799
m
202
0.3736
0.3849
238
mw+
300
0.3849
0.4354
1035
mst
301
0.4355

Y. KHAN, D. F~LDM~NN

CRYSTAL STRUCTURE OF SmCo,

215

Fig. 3. Photomicrographs of SmCo,, expected to be single-phase from Fig. I(c). (a) Grain boundary
etching, (b) grain surface etching, (c) Kerr domain pattern before etching. (d) Kerr domain pattern
after grain boundary etching.

216

Y. KHAN, D. F~LDMANN

TABLE II
ETCHING PROCEDURES
Ser. no.

Nature of etching

1.

Grain-boundary
of Fig 3(a)

2.

Grain-surface
of Fig. 3(b)

Etchants

Procedure

(A)

5 ~01% H,O,+

(Bf

10 ~01% corm. HCI

+85 ~01% H20.
5 ~01% cont.
HNU, + balance
C,HSOH.

30 s in etchant (A).
Washed out in H,O and
left in air for 5 mm.
IO min again in (A).
Washed in H,O and left in air again
for 5 min. Finally, 30 s in etchant (B)
and then washed out in &H,OH.

5 ~01% cont.
HNO, + balance
C,H,OH.
5 vol~ HF+
10 ~01% C,H,OH+
balance HrO.

30 s in etchant (A).
Washed out in H,O and
left in air for 10 min.
2 min again in (A).
Washed in H,O and finally 30 s in
etchant
and washed out in C,H,OH.

(A)

(B)

convening
neither

Srn,CO~ nor Sm,Co,, showed a homogeneous magnetic domain

structure as given in Fig. 3(c). This means that the samples consist of either
extremely large grains or fine grains with parallel orientation.
Etching was found to be very difficult and frequently gave the impression
that the whole of the polished sample was a single crystal. A sequential application
of various mixtures of etching agents (see Table II) finally led to a completely
different result, namely the occurrence of one phase precipitated in another (Fig. 3(a)
and (b)), with a fixed correlation between the o~e~tations of the magnetic axes
of matrix and pr~ipi~tes
(Fig. 3(d)). This metallographic examination clearly
supports the second possibility mentioned above, i.e., a two-phase structure of a
SmCo, alloy. An analogous phenomenon has been found by Jain et aLi in the
Cu-In system. The X-ray patterns of these two-phase SmCo, alloys may therefore be
interpreted as a superposition of the patterns of SmCo, with the CaZns-type
structure and of a new phase variant of the CaZn,-type structure having doubled
lattice constants (u = 9.995, c = 7.955, c/a = 0.795) and unchanged group-symmetry. A
comparison between calculated and observed sin e-values is given in Table III.
In order to check whether the atomic positions in the new CaZn, structure
sariant are greatly different from those in the CaZns-type structure, the relative
X-ray intensities of SmCo, were calculated on the basis of the CaZn,-type
structure and are given in Table I and Fig. 4. It is seen that the calculated
relative intensities of the main lines do not differ from the observed ones in the
composite diagram. This suggests that the atomic positions in the new phase variant
may not be much different from those in the CaZn,-type structure, and doubling
of the cell may take place by some process of faulting.
With this support for the existence of two phases in the composition range
between SmCo,, and SmCo,.,, which hitherto has been believed to be a homogeneity
region of SmCo5, experiments were done with the aim of obtaining either of the
two phases in the pure state, but neither variation in ~om~sition nor in heat-

CRYSTAL
TABLE
SmCo,

(NEW

Structure:

VARIANT)

TRANSLATION

GROUP

DATA

SmCo, (alloy annealed at 1000C for 72 h; powder 14 h 55OC/wa)

Guinier-photograph
with CoKcc. 4 h.
Calibrated
with Si for the following lattice-constants.
Hexagonal
with a = 9.995,s
c = 1.955,,
c/a = 0.795,,
Variant of the CaZns-type.
All reflexes permitted by the above mentioned translation
group are included.
no. = not observed.

(h k 1)
100
001
10 1.
110
200
111
002
201
102
120
112
21 I
202
300
301
003
103
212
220
310
221
113
302
311
203
400
222
401
213
312
004
320
303
104
321
402
410
114
411
223

217

OF SmCo,

III

Experiment

Remarks:

STRUCTURE

0.01069
0.01266
0.02335
0.03208
0.04277
0.04474
0.05063
0.05543
0.06133
0.07485
0.08271
0.0875 1
0.09340
0.09624
0.10890
0.11392
0.12462
0.12548
0.12832
0.13901
0.14097
0.14600
0.14687
0.15167
0.15669
0.17109
0.17895
0.18375
0.18877
0.18964
0.20253
0.203 17
0.21016
0.21322
0.21583
0.22172
0.22455
0.2346 1
0.23721
0.24224

Sin Oobs.

1. (Guinier )

n.0.
no.
0.02335
0.03207
0.04277
0.04463
0.05063
no.
n.0.
no.
no.
n.0.
0.09344
no.
n.0.
n.0.
n.0.
n.0.
0.12840
n.0.
n.0.
n.0.
n.0.
n.0.
no.
0.17118
0.17894
n.0.
no.
n.0.
0.20262
no.
n.0.
n.0.
n.0.
0.22180
n.0.
n.0.
n.0.
n.0.

n.0.
n.0.
vvw
vvw
W
VW

mw
n.0.
n.0.
no.
n.0.
n.0.
st
no.
n.0.
n.0.
no.
n.0.
m+
no.
X0.

n.0.
n.0.
no.
n.0.
mst
vst
n.0.
n.0.
n.0.
m
n.0.
n.0.
n.0.
n.0.
mw
no.
ll.0.

no.
n.0.
(continued)

218
TABLE

Y. KHAN.
III (contd.)

(h k 1)
204
313
322
500
412
214
501
403
330
304
420
331
421
005
323
502
105
224
510
413
332
314
511
115
422
205
404
503
512
600
215
430
601
333
324
431
305
423
520
414
521
602

D. FELDMANN

0.24530
0.25293
0.25380
0.26733
0.27519
0.27738
0.27998
0.28501
0.28871
0.29877
0.29940
0.30137
0.31206
0.3 1645
0.31709
0.31796
0.32714
0.33084
0.33148
0.33848
0.33934
0.34154
0.344 14
0.34853
0.35004
0.35922
0.37362
0.38125
0.38212
0.38495
0.39130
0.39564
0.39761
0.40263
0.40570
0.40830
0.41269
0.41333
0.41703
0.42708
0.42969
0.43558

Sin Oobs.

I, (Guinier)

0.24550
n.0.
n.0.
n.0.
n.0.
n.0.
n.0.
n.0.
n.0.
n.0.
0.2994
n.0.
n.0.
n.0.
n.0.
n.0.
n.0.
0.33094
n.0.
n.0.
x0.
n.0.
no.
n.0.
0.35004
n.0.
0.37373
n.0.
n.0.
0.38495
n.0.
n.0.
n.0.
n.0
n.0.
n.0.
no.
n.0.
n.0.
n.0.
n.0.
0.43550

vvw
n.0.
n.0.
n.0.
n.0.
n.0.
n.0.
n.0.
n.0.
n.0.
vvw
n.0.
n.0.
n.0.
n.0.
n.0.
n.0.
mno.
n.0.
n.0.
n.0.
n.0.
n.0.
mn.0.
m
n.0.
n.0.
mw+
n.0.
n.0.
n.0.
n.0.
n.0.
n.0.
n.0.
no.
n.0.
n.0.
n.0.
mst.

treatment at various temperatures gave one of the two phases alone. The only
conclusion we can draw from these experiments is that the observed three extra
X-ray diffraction lines become stronger with increasing Co-concentration. The investigation of single crystals of SmCo, is complicated by twin formation. This is
always expected in derivative structures *. The equilibrium phase diagram around
the composition of SmCo, and effects of the new phase on the magnetic
properties of SmCo, are being investigated 9,10. Moreover, the results of the heat-

CRYSTAL

STRUCTURE

Fig. 4. Calculated
camera.

powder

219

OF SmCo,

X-ray

intensities,

LS.40 for SmCo,

including

correction

for Guinier-type

treatment of the bulk as well as powder samples of the SmCo, intermetallic

compound do not agree with those found by Den Broeder and Buschow and
Westendorpt4, according to whom the SmCo, compound, as a single phase, is only
stable above 1080C (I&,) below which it decomposes into Sm,Co, +Sm,Co,,.
We annealed our samples (powder) for many hours at 550C (see Tables I and III),
but have not observed any such decomposition. A detailed study of the stability of
SmCo, will be presented in a separate paper.
ACKNOWLEDGEMENTS

The authors are indebted to Prof. E. Kneller for many stimulating discussions,
and to Dr. C. Herget of the Th. Goldschmidt A.G. for providing research material.

REFERENCES
1 J. Wernick and S. Geller, Acta Crysr., 12 (1959) 662665.
2 S. E. Haszko, Trans. AIM& 218 (1960) 763.
3 R. LeMaire, Cobair, 32 (1966) 117P125.

220
4
5
6
7
8
9
10
11
12
13
14

Y. KHAN, D. FELDMANN

K. Buschow, A. Van der Goot, J. Less-Common Metals, 14 (1968) 323-328.

F. Lihl, J. R. Ehold, H. R. Kirchmayr and Ii. D. Wolf, Acta Phys. Austr., 30 (1969) 164-175.
T. Shibata and T. Katayama, Japan J. Appt. Phys., 10 (1971) 510.
K. Sage& Iabelien zur S~rukturanalyse, Springer, Berlin, 1958, pp. 77-80.
M. H. Buerger, Crystal Structure Analyses, Wiley, London, 1960, pp. 53-69.
Y. Khan and D. Feldmann, to be published.
D. Feldmann, Y. Khan and M. Krone, Magnetic and X-ray investigations of SmCo, magnetic single
crystals, to be published.
W. Haucke, 2. Anorg. ANgem. Ckem., 244(1940) 17.
K. C. Jain, M. Ellner and K. Schubert, %r
die Phasen in der NIhe der Zu~mmensetzung
Cu.&,,,
to be published in 2. Meralfk.
F. J. A. Den Broeder and K. I-I. J. Buschow, J. Less-Common Metals, 29 (1972) 65.
F. F. Westendorp, Solid State Commun., 8 (1970) 139.