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J O U R N A L OF M A T E R I A L S S C I E N C E 17 (1982) 377--382

Magnetic susceptibility of heavy rare-earth

H. B. L A L *
Experimental Physik I V, Ruhr Universitat Bochum 4630 Bochum, West Germany

Department of Physics, University of Gorakhpur, Gorakhpur-273001, India

Results of the molar magnetic susceptibility (• measurements of heavy rare-earth (RE)

molybdates of the type RE2 (MOO4)3 with RE -- Gd, Dy, He, Er, Tm and Yb are
reported in the temperature range 3 to 300 K at a magnetic field of 3.2 X 10 s A m-1
All molybdates show ferrimagnetic behaviour with ferrimagnetic N6el temperatures
lying in the range 15 to 24 K. Evaluated magneton numbers agree fairly well with those
for free tripositive rare-earth ions. Various magnetic parameters are evaluated using
appropriate models.

1. Introduction Among the heavy rare-earth molybdates Gd, Tb,

Molybdates of the type RE2 (MOO4)3 (where RE = Dy and He usually crystallize in their a-form
Sc, Y and La to Lu) are some of the most important which is monoclinic [a-Eu2(WO4)3 type, space
compounds of rare-earth elements and some group C2/c] with four molecules per unit cell [6,
of them show interesting piezoelectric, ferroelec- 8]. The a-phase is stabilized only when both
tric, ferroelastic, fluorescent and non-linear opti- firing and annealing temperatures are kept below
cal properties [1-10]. The interest in these com- the a-t3 phase transition temperature, otherwise
pounds is recent and it is only in the last two the metastable /3' phase and the t3-phase co-exist
decades that reasonably pure rare-earth molyb- with a-phase. The rare-earth ion in such an (a-
dates were prepared, identified and studied. phase) arrangement is surrounded by eight oxygen
Obviously they are new compounds and non of ions at the corners of a slightly distorted cubic
the physical properties of the members of this cell. The molybdates formed with Er to Lu are
series are completely understood. Thus, the study reported to have orthorhombic structure, i.e.
of RE2(MoO4) 3 is interesting as well as impor- the are [Sc2(WO4)a] type, again with four mole-
tant. For the last few years a study into the mag- cules per unit cell. In such an arrangement, the
netic, dielectric and electrical properties of rare- rare-earth ion co-ordinates with six oxygen ions,
earch compounds such as sesquioxides [11-13], at the corners of a slightly distorted octahedral
tungstates [14-18], garnets [19-20], ortho- cell [61.
chromites [21, 22] has been undertaken, and
molybdates have been recently included in the 2. Material and experimental techniques
program. Some of the earlier studies on these com- The molybdates were prepared using the method
pounds are reported elsewhere [23-26]. The reported by Brixner et al. [8]. The starting mate-
present work reports low temperature (3 to 300 K) rials, for the preparation of Gd and Dy to Yb
magnetic susceptibility studies on heavy rare-earth molybdates, were the relevant sesquioxide
molybdates. [obtained from Rare-Earth Products, England,
RE2 (MoO 4)3 crystallise in variety of structures with a stated purity of 99.99 percent] and MoO3
depending upon the method of their preparation, [obtained from Bond, India, again with a stated
the annealing temperature used and the rare-earth purity of 99.99 percent] which were both dried at
ionic radius. The details are given elsewhere [10]. 200~ before use. Stoichiometric amounts of
0022-2461/82/020377-0652.60/0 9 1982 Chapman and Hall Ltd. 377
the starting materials were thoroughly mixed, type electromagnetic balance. The sample was
made into pellets and fired at 600 ~ C for 6 h in a suspended in the constant H(dHIdz)region using
platinum crucible in air. The reaction product was a copper sample holder, and the force exerted on
reground, again made into pellets and fired at the sample was recorded in the temperature range
700 ~ C for more than 24 h. The melting points of 3 to 300 K. Low temperatures were obtained by
the final products were found to be nearly the using a cryostat employing the continuous helium
same as those reported by other workers [10]. vapour flow method, and the temperature was
X-ray diffraction patterns of the prepared monitored using platinum (300 to 30 K) and
powders were taken using a CuK~ source at 295 K. carbon (40 to 30 K) standard resistors. Mohr salt
The diffraction patterns of Dy and Ho molybdates was used as a standard material for calibration.
were identified as being similar to those of the The details are described elsewhere [27].
a-Eu2(WO4)a type structure, whereas the diffrac-
tion patterns of Tm and Yb molybdates were 3. Results and discussion
found to be similar to those of the Sc2(WOa)3 The variation of inverse molar magnetic suscepti-
type (orthorhombic structure). The X-ray diffrac- bility, X~1 , with temperature, over the range 3 to
tion pattern of Er molybdate differs from that of 300 K of all the molybdates studied are shown in
Yb, but does not exactly resemble the pattern of Figs 1 to 3. The X~1 against T curves for all molyb-
Ho. Probably Er molybdate has some intermediate dates are almost linear above 100 K but at lower
structure, but no attempt was made to resolve temperatures show a downward drop towards the
the structure. temperature axis. Below 20 K all the curves again
Magnetic suceptibility of small sample (50 to show an extended and almost linear X~1 against T
100 rag) of the molybdates was measured using plot down to 3 K.
the Faraday method, employing a compensation The rare-earth ions are the only magnetic ions

0 20 4o 60 80 19~ .


IE 15

I0 O/ I ///~////,,/

rl~'e / " /"


/ ~/ / G~2(N~

-- . _
Figure 1 A plot of the inverse molar mag-
netic susceptibility x l ~ , against Tempera-
ture, T, for Gd~(MoO4) 3 powders in a field
of 3.2 • l0 s A m 1 T h e "experimental
points are shown by circles, the dotted lines
0 I I represent • calculated according to Equa-
0 Io0 2oo 300 tion 1 and the unbroken line represents
7"(K) xI'~ calculated according to Equation 2.