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\G 1990 Gordon ami Breach Science Publishers S.A. Printed in the 11nited States of America
OF SELEC'l'ED OOUBLE SULPHATES.
B. MROZ Institute of Physics, A. Mickiewicz Universlty, Grunwaldzka 5, 50-780 Poznan, Poland. J. A. TUSZYnSKI Department of Physlcs, University of Alberta, Edmonton, AB, Canada T6G 2J1. H. KIEFTE and M. J. CLOUTER Department of Physics, Memorial University of Newfoundland, St. John' 3, NF, Canada A1B 3X7,
Abstract Brillouin spectroscopy was used to study acoustic phonon softening in selected double sulphates whlch show interesting sequences of phase transitions leading to the appearance of the ferroelastic properties in these materials. Four crystals: LiCsSOq (LCS), LiKSOq (LKS), LINHqSOq (LAS) and LiRb5(SOq)3 1.5 H~SOq (LRSHS) were examined in the temperature ranges covering their transitions rnmm 4 21m at 202 K, 5mm 4 mm2 at 190 K, mmm(mm2) 4 21m at 285 K and ~mm 4 mm2 at 135 K, respectively. INTRODUCTION In several cases crystals which family exhibit ferroelasticity interesting leading to the appearance of the belong to of the the double phase
propertles, to it
is always associated with the onset of related
straln in the low-temperature phase phonon softening manifested In this paper we
the vanishing of one results of the
characteristic high of resolution the soft
component of the elastiC stiffness tensor. present Brillouin spectroscopy of the four ferroelastics: acoustic modes of the listed of materials. Brillouin The LeS, LKS, LAS and more elaborate concerning
LRSHS. We shall focus on the temperature dependences description of the results
experiments ~-7 these crystals can be found in our recent papers.
PROCEDURE AND RESULTS
All the studied crystals were
aqueous ratios. The The incident
solutions samples was The
containing the initial salts at stoichiometric has been described in detail elsewhere. produced scattered The of 90 by the single-mode was analyzed v light sound with were
were prepared in the form of cubes (5x5x5 mm). The argon-ion laser
piezoelectrically deduced from the
frequency shifts Av using the Brillouin equation, which in the case
scattering geometry takes the form:
where X is the wavelength of the incident light, n refractive indices for the inCident and respectively.
and ns are the 1 scattered beams, to the from for
The elastiC constants of the studied crystals related acoustic phonon propagating along the Q direction were the vanishing of the secular determinant:
the solution of the equation of motion, given by the condition
where qj' qk are the direction cosines of ~
the crystal. cijk1 are elastiC stiffness tensor components, 611 the Kronecker delta.
1. LiCsSO.q. (Les)
Les undergoes a continuous ferroelastic from the monoclinic orthorhombic the point group phonon group 21m. Such a acoustic the of transition
phase transition at to is the to associated the of
low-temperature with elastic twelve
softening of constant9.
to be strongly
11403 10.03 1). In on The from
temperature dependent. The frequency of this mode falls from GHz at room temperature to 1.41 GHz at 202.12 K (see addition, we have observed the effect of critical this mode, manifested by anomalous broadening temperature dependence of the c of Fig.
fluctuations this line.
elastic constant calculated 66 the measured frequency shift is given in Fig, 2,
s: 'E z
0 180 220 T!K)
FIG. 1. Temperature dependence of the soft acoustic mode of LeS (LKS) 4 LKS undergoes two ferroelastic 2, LiKS0
FIG. 2, The CBB elastic constant of Les vs temperature.
phase transitions from the hexagonal
to the orthorhombic syste~ 6jmmm ~ mmm at 940 K and 6mm ~ mm2 at about 190 K.5 The 6mm ~ mm2 transition is aSSOCiated with the softening of the mode related to the c
= 2. (c - c )· In fact, we found one of the e observed 60 l1 12 5 dependent, This mode Brillouin lines to be strongly temperature exhibits a strong hysteresis effect. The ~v(T) is almost a straight line while cooling whereas the effect of softening while heating, The frequency of this 188.4 K (see Fig, 3), Because of the the mode low soft is evident slowly GHz only from at ratio entire increases
9.81 GHz at 300 K to 10,02 at 223 K and then falls to 6.48 signal-to-noise mode in the below 190 K. we could not observe
temperature region studied. The dashed lines in the plots 8v(T) and coG(T) (Fig, 4) indicate the regions of extremely weak scattering.
3. LiNH S0 (LAS) 44
LAS is known to exhibit two ferroic ferroelectric
transitions: T1 = 460
namely K and
phase transition mmm ~ mmZ
B. Mroz one are
at al. at T2 285 the K.6 The both
~\ ! .,.
. __ ...L~
FIG. 3. Temperature dependence of the soft acoustic mode of LtS transition is associated
FIG. 4. The Coo elastic constant of LKS vs temperature. of the in the volume the acoustic T2 (see of the
with the doubling
unit cell. We have observed range from 273 to 293 softening. temperature 5). Because observe the temperature in Figure 6.
11 acoustic modes
temperature phonon linear Fig.
We dld not observe
The frequencies dependences mode
of all the observed modes exhibit
with a small step change at to the c
of the low signal-to-noise related dependences of transverse
ratio below T , we could not 2 elastic constant. The 44 elastic constants are given
FIG. 5. Temperature dependences of the transverse acoustic modes of LAS. A precursor observed
FIG. 6. Temperature dependences of the transverse elastic constants of LAS. phase
effect for the ferroelastic
transition of LAS 7 we
in the course of ultrasonic and
Schranz et ai .
Wys 10UZlI et ar ,
high-temperature vertical axis
that the intercept
indeed very close to T . 2
a T2 /
/ 360 440
following Schranz et al.~o
4. LiRb5(S04)3 1.5 H S0 (LRSHS)12 24 LRSHS exhibits a ferroelastic phase transition According studies13 transition to and the results of pyroelectric,
at about 135 K. open dielectric, the
change of point groups of this crystal is an still elastic properties
question. thermal phase
is of a ~ ~ mm2 type. The results of structural 15, 16 suggest that the room temperature phase is 4, with the studies 15 distorsion observed below Te' This is
with the theory of
in transitions9 the
which predicts the monoclinic For the ~ c We
phase 2 to
case when the prototype point group is tetragonal 4. ~ mm2 transition the Brillouin behavior in the case line related to the dependence.
elastic constant should exhibit strong temperature found such of one of the
I ~.2 ""1!
.1~ 0 100
The soft acoustic mode
FIG. 9. Temperature dependence of Cee elastic const. of LRSHS.
a L, GHz does at not
acoustic modes, The frequency 293 K to 2.11 GHz at 132 is strong 1 y temperature vanish at TC signifying This and other
of this mode falls from 5,06
elastic it the
(Fig. 9). However, features of all
an incomplete mode softening. crystals in part II of this paper,
studied shall be analyzed theoretically ACKNOWLEDGEMENTS
This research has been supported by grants Engineering Research Council of Canada Sciences, wroclaw, REFERENCES Poland.
1, E, Mr6z, T. Krajewski, T. Br~czewski, W. Chomka and D. sematowicz, Ferroe 1 ectrics, 42, 71 (1982.). 2. M. Wada, H. Shichi, A. Sawada, Y. Ishibashi, J. Phys, Soc. Jpn. 51, 32Jf5 (1982). 3. V. N. Anisimova, N. R. Ivanov, Kristallogr" _ll. 1018 (1986). 4. E. Mr6z, H. Kiefte, M. J. Clouter and J. A. TusZynski, Phys. Rev., B36, 31Jf5 (1981). 5, B. Mr6z, J, A. Tuszyrtski, H. Kiefte and M. J. Clouter, J. Phys. C (in print), 6. B. Mr6z, J. A. Tuszyrtski, H. Kiefte and M. J, Clouter, J. Phys. Cl, 783 (1989). 7. E. Mr6z, H. Kiefte and M. J. Clouter, Ferroelectrics, 82., 105 (1988). B. Mr6z, J. A. Tuszyrtski, H. Kiefte and M. J. Clouter, J. Phys. C (in print). 8. S. F. Ahmad, H. Kiefte M. J. Clouter and M. D. Whittmore, Phys. Rev" B26, q239 (1982). 9. ~oledano, M. M. Fejer and B. A. Auld, Phys. Rev., B27, 5717 (1983). 10. W. T. Schranz, K. Parlirtski, K. Warhanek and K. Zabinska, J. Phys" C20, 50QS (1987), 11. R. Wyslouzil, W. T. Schranz, A. H. Fuith and H. Warhanek, Z. Phys, , B64, 473 (1986). 12. A recent chemical analysis has led to the new formula for this crystal: Rb4LiH3(SOq)~ for which we have obtained a better fit of the measured denSity value to that calCUlated from the X-ray studies. 13. T. WOlejko, P. Piskunowicz, T. Br~czewski and T. Krajewski, Ferroe 1ectrics, 81, 175 (1988). 14. T. Wolejko, G. Pakulski and Z. TylczyrtSki, Ferroelectrics, 81, 179 (1988). 15. A. Pietraszko, K. Lukaszewicz, Zeit. Krisallogr., 185, 554 (1988) . 16. F. J; Zuniga, J. Etxebarria, G. Madariaga and T. Br~czewski, Acta Cryst. (to be published).
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