Physics of the Earth and Planetary Interiors, 14 (1977) 165—178 165

© Elsevier Scientific Publishing Company, Amsterdam — Printed in The Netherlands

ELASTICITY OF ALUMINATE, TITANATE, STANNATE AND GERMANATE COMPOUNDS

WITH THE PEROVSKITE STRUCTURE

ROBERT C. LIEBERMANN’, LEONIE E.A. JONES2 and A.E. RINGWOOD

Research School of Earth Sciences, Australian National University, Canberra, A.C. T. 2600 (Australia)

(Received November 22, 1976; accepted for publication January 31, 1977)

Liebermann, R.C., Jones, L.E.A. and Ringwood, A.E., 1977. Elasticity of aluminate, titanate, stannate and germanate
compounds with the perovskite structure. Phys. Earth Planet. Inter., 14: 165—178.

Ultrasonic data for the velocities of a large number of perovskite-structure compounds have been determined as a
a function of pressure to 6 kbar at room temperature for polycrystalline specimens hot-pressed at pressures up to
100 kbar in solid-media devices: ScAIO
3, GdA1O3, SmA1O3, EuAIO3, YA1O3, CdTiO3, CaTiO3, CdSnO3, CaSnO3
and CaGeO3. The elasticity data for these orthorhombic and cubic perovskites define systematic patterns on bulk
modulus (Ks)—volume (V& and bulk sound velocity (v~)—meanatomic weight (M) diagrams wInch are insensitive
to the details of cation chemistry and crystallographic structure. These isostructural trends are used to estimate
Ks 2.5 ±0.3 Mbar and v~,= 7.9 ±0.4 km/s for the perovskite polymorph of MgSiO3. On a Birch diagram of velocity
vs. density, the perovskite data define linear trends which lead to erroneous estimates of velocity for MgSiO3 unless
specific account is taken of ionic radius effects in isomorphic substitutions.

1. Introduction Using a diamond-anvil press coupled with laser

Perovskite-structure compounds have long been of
interest in materials science because of their ferro-
electric and piezoelectric properties. Because of the
very high intrinsic density of this structure type, the
possibility that (Mg,Fe)Si03 may exist in the perovs-
kite structure under the pressure and temperature
conditions of the earth’s mantle is also of considerable
geophysical significance. High-pressure studies on
analogue compounds such as CdTiO3 and CdSnO3
(Liebertz and Rooymans, 1965), CaGeO3 and CdGeO3
(Ringwood and Major, 1967), CaSiO3—CaTiO3 solid
solutions (Ringwood and Major, 1971), MnVO3
(Syono et al., 1971) and ScA1O3 (Reid and Ringwood,
1975) have supported the likelihood of this possibility.
1 .
Present address: Department of Earth and Space Sciences,
State University of New York, Stony Brook, N.Y. 11794, U.S.A.
2 Present address: Department of Geological Sciences, Harvard
University, Cambridge, Mass. 02138, U.S.A.
heating, Liu (1974, 1975a, 1976) has convincingly
demonstrated by X-ray diffraction studies that ferro-
magnesian silicate olivines, pyroxenes and garnets
with Mg/(Mg + Fe) ~ 0.3 (molar) transform to high-
pressure phase assemblages characterized by the
orthorhombic perovskite structure when subjected to
pressures in excess of 250 kbar. Liu and Ringwood
(1975) have shown that CaSiO3 undergoes a corn-
parable transformation at pressures greater than 160
kbar. The experimental synthesis of such high-density
phases suggests that perovskite is the dominant
mineral phase in the earth’s lower mantle (Liu, 1975b,
1976).
The ideal perovskite structure for ABO3 corn-
pounds has cubic symmetry with A ions at the cor-
ners, B ions at the center, and oxygen ions at the
centers
.
of the faces .of a cube. Thus,
.
the A and oxy-
gen ions form a cubic close packing with the B ions
in octahedral interstices. The A and B ions are dis-
tributed exactly as the Cs and Cl ions in the CsCl
166
lattice, and are surrounded by 12 and 6 oxygens,
respectively. Very few perovskite-type oxides actually
have this simple cubic structure at room temperature
(e.g., SrTiO3), but many assume this ideal structure
at higher temperatures (e.g., CaTiO3, BaTiO3). Both
CaGeO3 and CdGeO3 appear to have the cubic perovs-
kite structure at high pressure (Ringwood and Major,
1967; Prewitt and Sleight, 1969).
One of the most common variations of the ideal
perovskite structure is to orthorhombic GdFeO3
structure (Geller, 1956) with each unit cell built up
of four distorted perovskite units oriented diagonally
to thea03~B3~O
and b0 axes (Wyckoff, 1964; Galasso, 1969).
Many A compounds
3 have the GdFeO3 struc-
ture (Pbnm) including the GdAlO3, SmA1O3,
EuAlO3 and YA1O3 compounds of this study (Geller
and Bala,cell
rhombic 1956;
for Geller
CdTiOand Wood, 1956). The ortho-
GdFeO 3 differs slightly from thai of
the chosen space group is aofdifferent
3 the axes follow sequence,(Pc2
lower symmetry and
1n)
(Wyckoff, 1964, Vol. 2, pp. 412—413). There appears
to be somebydisagreement
exhibited CaTiO as to which symmetry is
3, CaSnO3
convenience they have been groupedand CdSnO3 but for
with CdTiO
Table II, p. 167. In either class of distorted ortho-3 in
rhombic perovskites, the A ion is in 8-fold and the B
ion in 6-fold coordination with respect to oxygen
(Geller, 1956; Marezio, 1969). The structures of
ScAlO3—MgSiO3 perovskites are similar to GdFeO3
and LuFeO3 (Marezio et al., 1970) with the A and B
ions displaced further from the ideal positions in
order to accommodate the smaller cations.
Depite the extensive knowledge of the crystallog-
raphy of perovskite-structure compounds and their
electric and magnetic properties, very little is
known about their elastic properties. This is particular-
ly unfortunate in light of the geophysical implications
discussed above because a detailed evaluation of the
role of perovskite phase assemblages in the lower
mantle requires a comparison with velocity models
derived from seismic studies. Specimens for ultrasonic
studies of the elastic properties cannot be produced
in the diamond anvil systems such as those employed
for the phase transformation investigations by Liu
because of the limitation of small sample volume. We
must, therefore, resort to large volume high-pressure
devices which have been used successfully to hot-
press polycrystalline specimens and to silicate analogue
compounds which crystallize in the perovskite struc-
ture at pressures less than 100 kbar.
As part of our continuing study of the elastic
properties of various mineral phases using specimens
hot-pressed at high pressures, we have previously
determined the compressional and shear wave veloci-
ties of a number of stannate and titanate perovskites
(Jones and Liebermann, 1974; Liebermann, 1976a).
The small range of molar volumes exhibited by these
compounds made it difficult to extrapolate to estimate
the elastic properties of MgSiO3-perovskite with
confidence. In addition, the effects of ionic radius and
details of the perovskite crystal structure on the
elastic properties needed to be evaluated. We selected
a series of aluminate perovskites for study because
they exhibited the 3~GdFeO3
(0.53 A) structure and the exceed
does not greatly radius
of octahedral Al
4~(0.40 A), as exemplified by the observed
that of Si 3~by Si4~in octahedral crystal sites
substitution of Al
(Ringwood et al., 1967; Reid and Ringwood, 1969).
ScAlO3 is particularly important as a model composi- 3~
tion because the (octahedral).ionic radius
2~(0.72ofA)
Scand
(0.73 A) is between
2~(0.77 A) and it the
has radii
beenofsynthesized
Mg in the
Fe
perovskite structure at 1,000°Cand 120 kbar (Reid
and Ringwood, 1975). We also investigated CaGeO
3
and CdGeO3 because of their demonstrated usefulness
as models for the elasticity of their silicate analogues
with pyroxene and garnet structures (Liebermann, 1974)
and their known transformation to the perovskite
structure at high pressure (Ringwood and Major,
1967; Prewitt and Sleight, 1969).
The purpose of this paper is to present these new
elasticity data for compounds with the perovskite
structure, to investigate systematic relationships
between the elastic and crystallographic properties of
these isostructural compounds, and to use these
relationships to estimate the elastic properties of
MgSiO3 perovskite.
2. Experimental procedure and data
Powder samples of ten chemical compounds were
prepared from the component oxides by heating at
atmospheric pressure. Details of the sin tering proce-
dures are given in Table I as are the crystallographic
structures of the synthesized powders. The ScAlO3
 167

TABLE I
Details of preparation of hot-pressed specimens of perovskite-structure compounds
3)
Compound Starting material *1 Hot-pressing conditions Density (g/cm
synthesis T time structure P T time bulk % X-ray
CC) (h) (kbar) CC) (h)

ScAIO
3 — — amorphous *2 30 1,150 2 4.15 96.6
GdA1O3 1,200 18 perovskite *3 20 1,000 1 7.32 98.4
SmAlO3 1,200 18 perovskite *3 20 1,000 1 7.01 97.8
EuA1O3 1,200 18 perovskite *3 20 1,000 1 7.07 97.6
YAIO3 1,200 18 perovskite *3 20 1,020 1 5.09 95.1
CdTiO3 1,200 6 perovskite 25 800 1.5 6.11 96.5
CaTiO3 1,200 6 perovskite 17 1,000 1 4.01 99.1
CdSnO3 1,200 6 perovskite 15 1,000 1 7.38 96.9
CaSnO3 1,200 12 perovskite 15 800 1 5.47 98.3
CaGeO3 1,300 4 pyroxenoid— 100 1,000 2 4.87 94.2
wollastonite

*1 Unless otherwise stated, compounds synthesized by mixing component oxides and sintering in air at atmospheric pressure.
*2 See Reid and Ringwood (1975) for details of preparation; starting material prepared by C. Li and A.F. Reid of CSIRO, Division
of Mineral Chemistry.
*3 Even after re-grinding and re-sintering, pure perovskite phases were not observed. Only after hot-pressing at 20 kbar did the non-
perovskite lines disappear.

powder was prepared by C. Li and A.F. Reid of the The titanate, stannate and germanate compounds
Division of Mineral Chemistry of CSIRO, Melbourne were straightforward to synthesize with the
and was amorphous to X-rays. perovskite structure, but the Gd, Sm, Eu and Y

TABLE II
Crystallographic data for perovskites *1

Compound Lattice parameters (A) 3/mole)

Molar volume weight
Molecular (g/cm3)
Density Reference *2
a b C (cm (g)

ScAlO
3 4.933 5.226 7.193 27.92 119.99 4.297 (1)
GdAIO3 5.247 5.304 7.447 31.21 232.33 7.445 (2)
SmA1O3 5.285 5.290 7.473 31.46 225.33 7.162 (2)
EuA1O3 5.271 5.292 7.458 31.32 226.94 7.246 (2)
YA1O3 5.179 5.329 7.370 30.63 163.89 5.350 (2)
CdTiO3 5.301 7.606 5.419 32.90 208.30 6.331 (3)
CaTiO3 5.367 7.644 5.444 33.63 135.98 4.043 (4)
CdSnO3 5.547 7.867 5.577 36.65 279.09 7.615 (5)
CaSnO3 5.519 7.885 5.668 37.14 206.77 5.567 (6)
CaGeO3 5.265 5.265 7.446 31.08 160.67 5.170 (7)
BaTiO3 3.989 — 4.029 38.61 233.24 6.040 (3)
SrTiO3 5.520 5.520 7.808 35.84 183.52 5.121 (3)

*1 All compounds have orthorhombic siructure (Z = 4) with exceptions of CaGeO3 and SrTiO3 which appear to be cubic; corre-

sponding orthorhosubic cell parameters are taken as a = b = a0 ~J2, c = 2a0 [see also Prewitt and Sleight (1969), Reid and
Ringwood (1975)], and BaTiO3 which is tetragonal (Z = 1).
*2 Reid and Ringwood (1975); 2 Geller and Bala (1956); 3 = Roth (1957); 4 = Robie et al. (1966); 5 = Smith (1960);
6 Smith and Welch (1960); 7 = Ringwood and Major (1967).
168

aluminate mixtures contained unreacted oxides des- I I I

pite repeated grinding and re-sintering.
Polycrystalline specimens of these ten compounds - -

with the perovskite structure were then hot-pressed - p increasing -

in piston-cylinder (P< 35 kbar) or squeezer (P ~ — P decreasing._

<120 kbar) solid-media apparati. A comprehensive ~, -

description of the hot-pressing techniques employed -

in our laboratory is given elsewhere (Liebermann et al Compressional

1975, 1976). The exact pressure and temperature -~ ~~i® -

conditions for the fabrication of the polycrystalline > — Sh 50

specimens (given in Table I) were selected to be well -

inside the thermodynamic stability field of the -

relevant phase desired (Liebertz and Rooymans, - -

1965; Ringwood and Major, 1967; Reid and Ringwood, I I

1975). In the case of ScAlO
3, we found that it trans- ~ 1 2 3 4 5 6

formed completely to the perovskite structure at Pressure,kbar

0 I I I I
P= 30 kbar for T= 1,150 C, far lower than the syn- - -

thesis pressure reported by Reid and Ringwood - GdAIO3

(1975). We were unsuccessful in transforming CdGeO3 - -

to the perovskite structure at P 100 kbar and T - 0 P increasing -

1.000°C. 60 P decreasing
After sin tering for 1—2 h at elevated pressure and —~ - -

temperature, the run was slowly quenched (20—60 - Compressional -

mm) so as to retrieve polycrystalline aggregates ~- ~®~® 0,,~ OX0 ®~0 0 -

which are not only single phase but also free of - -

macroscopic cracks and suitable for ultrasonic measure- 65 — o— 4~0

ments. The crystallographic structure of the speci- II
mens recovered at ambient conditions was confirmed L ® -

by comparison of X-ray diffraction photographs with L- -

patterns from the literature (Table II); even the Gd, I I I I

0 1 2 3 4 5 6
Sm, Eu and Y aluminates, which had proved difficult
to synthesize in the perovskite structure at atmospher- - B Pressure kbar
ic pressure, transformed readily underP= 20 kbar. 7C I I
Bulk densities determined by the Archimedes method ~ -

and single-crystal densities are given in Tables I and ~ _ flSA

These polycrystalline specimens are less than 4% CO~P~SS~~I
porous (except YAIO3 and CaGeD3) and have a grain 6-5 — —

size less than 50 pm. They are of cylindrical shape -

with diameter 3 mm and lengths 0.8—3.9 mm. E - P increasing -

The compressional (vp) and shear (vs) wave veloci- - ~ decreasing -

ties in our recovered specimens were measured by the - -

ultrasonic pulse transmission or pulse superposition > 60 — C —

techniques as modified for our small specimens - Shear 0

(Liebermann et al., 1975). The precision of the veloci- - ~‘~° -

ty measurements by the pulse transmission method is -

±2%and we have employed this technique for most - I I I

of the specimens in this study; we have reduced the 0 1 2 3 4 5 6

error introduced by the calibration of the oscillo- © Pressure kbar

 I I I I I I I
— EuAIO
3 - — -

- - - CdSnQ3 -

— - — 0 P increasing -

- - - x P decreasing -

— Compressional C ~ 65 —

- -~ - - Compressional -

7/ - ~- - 0 Ox® Ox® OX® Ox® Ox

- X

- ~. 7 -

> 65 Shear —. 40 . - -

® Ox® Os® Ox 60 — Shear

C *0 ®xO OCO Ox® ox® ®~

- 0 P increasing -

- ii P decreasing -

0 ~ 0 ~ 6~°
Pressure kbar © Pressure, kbar
85 I I I __________________________________________
I I I

- vA103 - _ CaSnO3

- Compressional ® ~o -

8-0~~C ®
—
Compressional C OX ® 0R
- - - — — C® 0 —

E - 0 P increasIng - ~ ® C ®
E - x®
- ii P decreasing - -~ ® p increasing
- - ~. —/ x P decreasing

> 75 — C® ®C® ®~ .2 /
- C® Shear - 6~
o Shear ox

C® 640 ~x® ®~ ®x®

Pressure, kbar 0 1 2 3 4 5

I I I I Pressure , kbar

—
— CaTiO3 -
- -
I I

- - CaGeO3

9-0 — — 5.5 Compressionol

- -
- 8—,,, ~. —

E — Cempressional ®C0 C

~~
— ®C C 0 5~5®5®~® Shear
x~x®x®C0CflC® 7- E- —-
- 0 0 ® Z
X direction
direction -
-
> 8-~ ~®~®~®~® ® 0 — 50 0 - -
- -

— ® P -increasIng
.
—
> 7— —5

— C P decreasing - Shear -

I— . . . . . S • • •~
— — I • S 0 ® 0
I I I I ®®
0 1 2 3 4 5 6 j~® -

0 Pressure, kbar - I I
0 1 2 3 4 5 6
Pressure , kbor

Fig. 1. Compressional and shear velocities vs. pressure at room temperature for polycrystalline specimens of perovskite-structure
compounds listed in Tables I and III using the ultrasonic pulse transmission or pulse superposition techniques; precision of individ-
ual velocity determinations is ±2%for the former (A—D and F—I) and ±0.5%for the latter (F) techniques.
 0
170

o ~
-~

~. if) ~. if) ~- — — ~. ~. ~. — —

~ C C C
+1 +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 +1
—C_~0,0or--
II CN———a,C00a,C~—
a-

a
-u
o
E
.9 +~+1 +~ +1 +1 +1 +1 +1 +1 +1 +1 +1
-~ ~
N O\ oo en ~ N
en~q—t-r- r— ~O C 00 r— ~ II

a; N — — N N N — ‘a — — — —
a
Cs 0
C00Nr—00r-.1-irIen000000 E
a — .-I

Is
a
if) .-~00 a, — a, N ~ C a, r— en

a N ~r ‘~p i~ ‘a in ‘a ~- if) ~& if) if)

a
a.
C000000a,Nenr~-ooa,r-sN 0
.-~CCCCCCCCCCC
CCCCCCCCCCCC
+1 +1 +1 +1 +1 +1 +1 a +1 +1 +1 a en
‘.Ci — en ‘a N ~ N — N O~in CO —
N
~ en en ~ en in en ~- ~ en ~- N
d
— z
CCCCCCCCCCCC -~

+1 +1 a +i +1 +1 +1 +1 +1 +1 +1 +1
if) in ~ a, N ‘a ~ N N if) N en
a N N N a, — en oo en a, — ~o ~ ~
a 0~00~-0O’a00~O00

er
‘a 00 N N if) ‘a a, ‘a 00 sO
a, a, a, a, a, a, a, a, a, a, I I

.)si if) N — N ‘a — 00 N N
E -~ ~~en~o0
-Q .0 ~ N N N if) ‘a ~ N if) ~ I I a
Cs

a .•~ ~, ‘a if) N ‘a C en if N C C — —i
a a, ~ ‘a ‘~ in en ~ ‘a ‘a N ~ N 00
a hi~ N ~ — N en en C ‘a if) — C ‘a .—
~

N — ‘a N en C en i~ ~. 00 — ~- Is
o ~
Cs N — — C N en ‘a N — 00
— If)
Nenenenenenenenenenenen
,~

a.
o C if) N a, 00 ‘a C N if S en if) ©
Q~C~00en~ON ‘a~a.0
‘a if) if) N — N if) — N ‘a ‘a N 0) ~‘

a
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~
0 ~O~O OIs~IsIsC5i., ~
00 Li 00c~00a;~c)ç)QL)Q~00 * * * *
 171

scope time base by using a reference frequency to
measure the transit time in the specimen (following
Mattaboni and Schreiber, 1967).
The pressure dependence of v~,and u~was de-
termined as a function of hydrostatic pressure to 6
kbar at room temperature, as illustrated in Fig. 1;
the data for CdTiO3 have been reported previously
(Liebermann, 1976a). In general, both and v~in-
crease systematically with increasing pressure and
these changes are completely reversible on release
of pressure. Although in most of the specimens the
velocities have been measured only along the cylin-
drical axis of hot-pressing, specimens fabricated in
such a manner have been shown to be elastically
bulk modulus Ks is inversely proportional to the
volume for isostructural sequences of alkali halides,
fluorides, oxides, and other chalcogenides (e.g., O.L.
Anderson and Nafe, 1965; D.L. Anderson and O.L.
Anderson, 1970). In Fig. 2, we plot the perovskite
data in a diagram of log Ks vs. log V
0, where V0 is
molar volume. There is considerable scatter, but the
data are sufficient to establish the vertical position of
a KsVo = constant isostructural line for perovskites.
Shankland (1972) and Chung (1972) have derived
an equation relating the bulk sound velocity u~to
mean atomic weight M from elementary Debye
theory of solids:
—

isotropic (Liebermann et al., 1975, 1976). Further- ~ In v~/alnM)x = (1)

more, for GdAlO3, CaTiO3 and CaGeO3 (Fig. 11), for constant crystallographic structure X; as this
we have measured the velocities in a direction equation relies on the KsV0 = const. law for isostruc-
transverse to the cylindrical axis and demonstrated tural sequences, it is complementary to the patterns
that the specimens are isotropic within the precision of Fig. 2. The perovskite data are plotted in a diagram
of the data. of log v~vs. log Mm 2= Fig. 3. The
const. fitisofperhaps
trend the data to an
even
We take theof
representative axial velocity
those of thedata atP= 6 kbar
zero-porosity to be
elastically- isostructural v~M”
better than in the Ks—V
0 diagram (Fig. 2).
isotropic polycrystalline aggregate. The CaGeD3 A particularly noteworthy feature of Figs. 2 and 3
specimen was fabricated in a uniaxial press and may be is that the aluminate, titanate, stannate and
anisotropic at low pressure due to the presence of germanate data may be represented by the same iso-
laminar cracks (Liebermann et al., 1976) and thus, we structural perovskite trends. This independence of tho
have adopted the mean of the axial and transverse
velocities at 6 kbar for this specimen. Using the X-ray
density, we calculate the adiabatic elastic moduhi 3 \ I I I
and the Poisson ratio from the equations for an iso- N
tropic elastic medium (Table III). We also included — ‘~ M55103 ,.— K5V~- const. —

the room temperature data for SrTiO3 which has ~

the ideal cubic perovskite structure and for BaTiO3
which has a tetragonal symmetry. 2 —

3. Discussion
I
~ F5 — -

In recent years, there has been considerable effort ® Al

in solid-state geophysics to establish patterns relating • Ti, Sn, Ge
the elastic properties to other physical properties such
as molar volume, density and mean atomic weight for 1 I
compounds belonging to the same crystal class. In 20 30 40
3/mole 50
thisseveral
fit section,
of we show
these how our newpatterns
semi-empirical perovskite
and data Molar volume, cm /
demonstrate the usefulnesss of such trends by esti- Fig. 2. Log-log plot of bulk modulus Ks vs. molar volume V
0
for compounds with the perovskite structure. Dashed line
mating the elastic properties of MgS1O3 perovskite. KSVO Cs constant is theoretical prediction for isostructural
Several previous investigators have shown that the series (e.g., D.L. Anderson and O.L. Anderson, 1970).
172
9 I I I
Cs 8 IMeso,
- ~ ® ~
— .•
- I-
~ ~.c?
05— ~—
0 Al ~ G ~-
- • i~ n~ e
~15 20 30 40 50
Mean atomic weight . Simmons, 1972).
Fig. 3. Log-log plot of bulk sound velocity u~vs. mean atomic
weight Mfor compounds with the perovskite structure. Dashed
line = constant is theoretical prediction for isostructural
series (following Shankland, 1972 and Chung, 1972).
isostructural patterns from details of cation chemistry
has also been observed for the rutile, garnet, ilmenite,
pyroxene, olivine and spine] structures (Liebermann,
1970, l972a. b, 1973a, b, 1974, 1975, l976b). We
conclude that germanate, titanate and stannate com-
pounds, which have been so important as models of
the crystal chemical properties of their silicate ana-
logues, are also usefulmodels for the elastic properties.
There is also no indication in Figs. 2 and 3 of
different isostructural trends for the various forms
of the perovskite structure; the titanates and stannates
with the CdTiO
3 structure are not distinct from the
aluminates with the GdFeO3 structure. Nor are SrTiO3
(cubic), CaGeO3 (cubic) and BaTiO3 (tetragonal)
anomalous. Thus, any dependence of elasticity upon
symme try or coordination within these oxide perovs-
kites lies within the scatter of the existing data.
The isostructural trends of the K5V0 = const. and
= const. laws are applied in Table IV to estimate
the elastic properties of MgSiO3 perovskite using the
molar volume determined
3/mole, and M= by Liug.(l975a)
20.08 of Vm
Both laws lead=
24.59 cm
to estimates of K5 = 2.5 ±0.3 Mbar and v~= 7.9
±0.4 km/s if the uncertainties are based on the maxi-
mum permissible range due to the scatter of the data in
Figs. 2 and 3. These mean estimates are considerably
lower than those given previously (Ks = 2.8 Mbar, V45 =
8.3 km/s) based only on the data for CdTiO3 and
CdSnO3 (Liebermann, 1976a). We have also tentative-
ly estimated that tj~,,= 10.4 ±0.5 km/s for2=MgSiO3
const.
perovskite on the assumption that v~M”
I Birch (1961) suggested that the compressional
— velocity u~decreases linearly with increasing density
- for minerals with the same crystallographic structure,
- and others have extended this to describe the bulk
sound velocity v~,(McQueen et al., 1964; Wang,
- 1968, 1970). Subsequent investigators have verified
these suggestions for isomorphic substitutions of Fe
—
for Mg and Al in the corundum, spine], olivine and
pyroxene lattices (Chung, 1970, 1971; liebermann,
60 1970, l972a, 1973b; Akimoto, 1972; Wang and
In Fig. 4, we plot the perovskite data in a composite
Birch diagram for Up, v~,and v~vs. p. With the excep-
tion of CaSnO
3 and BaTiO3, the data define trends
which could be extrapolated to estimate u~= 9.1,
= 5.0 and3).
v~1,These
= 7.0 km/s for MgSiO3
estimates perovskite
of v~and v~are (p =
4.083 g/cm
markedly lower than those derived in Table IV which
dramatically illustrates the pitfalls of extrapolations
wh,,ich have no theoretical basis. As Shankland (1972)
has shown, the velocity—density relationship along
isomorphic sequences obeying the v~M1”2= const.
law should be:
‘~1 \ r ‘a 1 “ ~
( fl V~ = —i Ii — ( ‘~_~1~) I (2)
a l~~ /x 2 L ~ ~ in M
Clearly, a unique (~3ln v~/aln P)x trend will only
exist for those isomorphic substitutions for which
(~ ln Vm/a lnM)x const. ln Fig. 5, we plot log Vm
vs. logM for the perovskite-structure compounds of
this study along with the (Mg,Fe)Si03 perovskites of
Liu (1976): no single trend exists, and relative to
MgSiO3 values of (~ ln Vm/a ln M) range from 1/6 for
MgSiO3—(Mg05Fe05)Si03 to 1 for MgSiO3—CaTiO3.
Thus, no unique trend should exist for v~p—pin
Fig. 4 and the apparent linearity is fortuitous. How-
ever, as the arrows in Fig. 4 demonstrate, estimates of
V45 for MgSiO3
compounds based
(e.g., on eq. 2 from many isostructural
CaT1O
3, CaGeD3, CaSnO3, EuAIO3)
all converge to consistent values of v4, = 7.9 ±0.5
km/s. Similar remarks hold for v~,from the calculations
of Table IV and the trends also indicated by the
arrows in Fig. 4.
In the light of the apparent inconsistency be-
tween the v45 trends of Figs. 3 and 4, a few remarks
on our past use of such diagrams are perhaps
appropriate.
and v Liebermann (1974) used log V45—logM
45—p diagrams to obtain compatible estimates
 173

TABLE IV -

Parameters for law of corresponding states and Shankland-Chung relationship for perovskite-structure compounds and estimated
3/mole;M 20.08; p = 4.083 g/cm3)
elastic properties for MgSiO
3 perovskite (V0 = 24.59 cm
Compound K
5V0 3 mole_i) (km s~ g/z)
v45JVt~’2 MgSiO3 perovskite ~
(Mbar cm K
5 U45

(Mbar) (km s~)

ScA1O3 64.8 5.3

± 36.0 ± 1.2 2.6 8.0
GdA1O3 55.9 4.7
± 33.5 ± 1.4 2.3 7.5
SmA1O3 56.0 ± 4.4 33.4 ±1.3 2.3 7.5
EuAIO3 63.4 ± 4.7 35.6 ± 1.3 2.6 7.9
YAIO3 62.5 ± 4.6 35.0 ± 1.3 2.5 7.8
CdTiO3 69.8 ± 1.3 37.4 ± 0.4 2.8 8.3
CaTiO3 59.5 ± 1.0 34.5 ± 0.3 2.4 7.7
CdSnO3 68.2 ± 4.8 36.9 ± 1.3 2.8 8.2
CaSnO3 55.7 ± 5.6 33.4 ± 1.7 2.3 7.5
CaGeO3 61.5 ± 4.7 35.1 ± 1.3 2.5 7.8
BaTiO3 68.3 ± 1.5 36.7 ± 0.4 2.8 8.2
SrTiO3 62.4 ± 1.4 35.3 ± 0.4 2.5 7.9

Mean 62.3 35.2 2.5 ± 0.3 7.9 ± 0.4

~ Errors in K~V0 and ~M½ contribute uncertainties of about 0.2 Mbar and 0.3 km/s to individual estimates of K5 and U45 of
MgSiO3 perovskite.

of v45 for the garnet and ilmenite polymorphs of for the olivine structure using data for gerrnanates and
MgSiO3 based on data for germanate compounds silicates and for the spinel structure using data for
with these structures. Similar behaviour was observed germanates, silicates, aluminates and ferrites
(Liebermann, l973a, 1975). In all of these cases, the
1 I I I isomorphic compounds define a single linear trend
M95.0 ~ Pe,xvskiie, on a log Vm~lO0M diagram such as Fig. 5 (see also
- - Vp - Shankland, 1972, fig. 1) and a unique v45—p pattern
9 - ~ - - - could be expected. For the rutile and ilmenite
~ structures, however, the titanate—stannate corn-
- M9S4 ~ 0

~ ~__~N_ - ~4O I I
- o --

~ Dens,ty, g/ix,3
~
Fig. 4. Birch diagram of velocity u vs. density p for compounds
~OM~O3

20 20 30 40 50 60

with the perovskite structure. Apparent linear v—p trends Mean atomic weight . g
lead to much lower estimates for the velocities of MgSiO3 Fig. 5. Log-log plot of molar volunie V0 vs. mean atomic
perovskite than those predicted in Table IV on basis of Ks V0 = weight M for compounds with the perovskite structure. Data from
const. or v45M’1’2 const. relationships (see arrows). Table II except for (Mg,Fe)Si03 from Liu (1976).
174

pounds define trends on a v

45—p which diverge from
those exhibited by their germanate—silicate iso-
morphs (Liebermann, 1973b, l976b); this behaviour
is consistent with the different Vm~Mdependence
of these isomorphic substitutions [see also discussion
in Shankland (1972) and Shankland and Chung
(1974)]. We also note that the anomalous v—p
behaviour of Ca-bearing (Birch, 1961; Simmons, 1964)
and Ti-bearing (Birch, 1961; Soga, 1967) minerals
are merely special examples of the importance of
ionic radius considerations in governing the effect
of isomorphic substitution on the elastic wave veloci-
ties (D.L. Anderson, 1969; Shankland, 1972).
On the basis of moduli—volume and velocity—mass
systematic relationships,
properties of MgSiO we may estimate the elastic
3 perovskite as given in Table V.
These estimates must be regarded as tentative but
may prove useful until direct measurements of the
elasticity of silicate perovskites become available,
most probably from Brillouin scattering experiments
of the type described by Weidner and Carleton (1977)
for a 100-pm single-crystal of coesite.
As a result of Birch’s (1952) suggestion that the
and density ratios of several perovskite-structure
compounds.
In Table VI, we have listed the elastic properties
of six perovskite-structure fluorides and of the iso-
chemical fluoride and oxide mixtures of the perovskite.
structure compounds of this study. Following Davies
(1974, 1976), we have plotted those data in Fig. 6
as a function of bulk sound velocity ratio vs.
density ratio (perovskite/mixture). For the Cd
compounds, we have used the elasticity data for a
polycrystalhine specimen of CdO hot-pressed in our
laboratory and presented in Fig. 7; the measured
elastic moduli (K5 = 1.11 Mbar, p = 0.66 Mbar) are
considerably
976Ksdifferent than
= 1.31 those
Mbar, p =estimated by on
0.49 Mbar)
Davies (l
the basis of elasticity systematics.
1 3
I
0 FIuori~s
x Oxides
1~2 — 0

lower mantle might be composed of a mixture of

dense-packed oxides with the rocksalt and rutile 0

structures, this “mixed-oxide” phase assemblage has 0

become a standard reference against which to compare

the densities of other possible mantle mineralogies. 11 — —

Recently, Davies (1974, 1976) has also used the MgS~0 0 0

mixed-oxide state as a reference for the elastic x

properties. The perovskite structure is one of the very v.P/vIM

few which are intrinsically more dense than the iso-

chemical mixture of rocksalt- and rutile-structure
oxides, and Davies (1976) discussed briefly the velocity

TABLE V
Elastic properties of MgSiO3 perovskite 0•
F05 1.10 1.i5

Molecular weight M 100.41 g

Mean atomic weight M = 20.08 g 3/mole *i Fig. 6. Normalized plot of bulk/ sound velocity v
Molar volume Vm = 24.59 cm3 45 vs. density
p for oxide and fluoride compounds with the perovskite struc-
Density
Compressional velocity p = Cs4.083
Up 10.4 ±
g/cm
0.5 km/s ture (following Davies, 1974, 1976). The data are normalized
Shear velocity v~= 6.0 ±0.5 km/s to the values of and ~M (data of Table VI) for the iso-
Bulk sound velocity v
45 = 7.9 ±0.4 km/s chemical mixtures with the rocksalt and rutile structures.
Bulk modulus KS Cs 2.5 ±0.3 Mbar Datum for MgSiO3 perovskite based on estimates in text and
Shear modulus ~.m
= 1.5 ±0.2 Mbar calculated properties of MgO rocksalt plus Si02 rutile (Table
VI).
‘~ Liu (1975a).
 175

TABLE VI
Elastic properties of perovskite-structure fluorides ‘~ and of isochemical fluoride and oxide mixtures *2 of perovskite-structure compounds

Compound Structure M Vm 3/ Density Velocity (km/s) Elastic moduli (Mbar) Poisson Refer-
(g/cm3) ratio ence *3
(g) (cm
mole) Up v~ v
45 Ks

KMgF3 rocksalt + 24.08 42.60 2.826 5.70 3.19 4.35 0.51—0.56 0.27—0.30 0.272 (1), (2)
rutile
perovskite 24.08 38.23 3.150 6.69 3.94 4.90 0.76 0.49 0.234 (3)
KNiF3 rocksalt + 30.96 43.08 3.593 5.06 2.72 3.98 0.54—0.59 0.27 0.297 (1), (4)
rutile
perovskite 30.96 38.84 3.986 6.05 3.36 4.62 0.85 0.46 0.277 (5)
KCoF3 rocksalt + 31.01 44.11 3.515 4.86 2.67 3.76 0.49—0.51 0.25 0.284 (1), (6)
rutile
perovskite 31.01 40.58 3.820 5.79 3.11 4.54 0.79 0.37 0.297 (5)
KMnF3 rocksalt + 30.21 46.68 3.236 5.03 2.63 4.01 0.51—0.53 0.22 0.312 (1), (7)
rutile
perovskite 30.21 44.16 3.420 5.58 3.02 4.36 0.65 0.33 0.293 (8)
RbC0F3 rocksalt + 40.28 48.30 4.170 4.15 2.24 3.24 0.42—0.45 0.20—0.22 0.294 (9), (6)
rutile
perovskite 40.28 42.34 4.757 5.29 2.89 4.11 0.80 0.40 0.287 (5)
RbMnF3 rocksalt + 39.48 50.85 3.882 4.28 2.22 3.43 0.44—0.47 0.19 0.316 (9), (7)
rutile
perovskite 39.48 45.73 4.317 5.12 2.82 3.95 0.68 0.34 0.282 (10)
CdTiO3 rocksalt + 41.66 34.24 6.082 6.73 3.81 5.09 1.58 0.88 0.264 (11), (12)
rutile
CaTiO3 rocksalt + 27.20 35.43 3.838 8.64 5.00 6.42 1.58 0.96 0.248 (13), (12)
rutile
CdSnO3 rocksalt + 55.82 37.14 7.515 6.03 3.36 4.62 1.59—1.61 0.85 0.275 (1]), (14)
rutile
CaSnO3 rocksalt + 41.35 38.31 5.397 7.25 4.13 5.46 1.61 0.92 0.260 (13), (14)
rutile
Cat7eO3 rocksalt + 32.13 33.42 4.807 8.13 4.80 5.96 1.68—1.73 1.11 0.232 (13), (15)
rutile
BaTiO3 rocksalt + 46.65 44.26 5.270 5.83 3.32 4.39 0.97—1.07 0.56—0.61 0.260 (16), (12)
rutile
SrTiO3 rocksalt + 36.70 39.43 4.654 7.10 4.14 5.25 1.26—1.31 0.79—0.81 0.242 (13), (12)
rutile
Mg$iiO3 rocksalt + 20.08 25.28 3.972 10.40 6.49 7.21 2.06 1.67 0.181 (17), (18)
rutile

*1 Isotropic moduli and velocities calculated from the single-crystal elastic moduli by the Voigt-Reuss-Ilill procedure.
*2 Elasticity of mixtures calculated from known properties of rocksalt- and rutile-structure components using the mean of the Hashin-Shtrikman
(1963) bounds; both bounds are given where spread is greater than 0.01 Mbar.
*3 References for elasticity data:
1 = Marshall and Miller (1967) 7 Cs HaussOhl (1968) 13 = Son and Bartels (1972)
2 Cs Jones (1977) 8= Aleksandrov et al. (1966) 14 Cs Chang and Graham (1975)
3 Cs Jones (1976) 9 Cs Cleavelin et al. (1972) 15 Cs Wang and Simmons (1973)
4 Cs Wu (1976) 10 = Melcher and Bolef (1969) 16 Cs Vetter and Bartels (1973)
5Cs Rousseau et al. (1974) JJ Cs this paper (Fig. 7) 1 7Cs Spetzler (1970)
6 Cs Hart and Stevenson (1970) 12 Cs Manghnani (1969) 18 = Liebermann et al. (1976)

The oxide and fluoride perovskites exhibit a
wide span of density ratios (1.01—1.15) and all have
higher bulk sound velocities than the isochemical
mixtures (CaSnO3 excepted). Despite the scatter of
the data in Fig. 6, the average slope (~ ln v45/a ln p)
is about 2. Thus we would expect MgSiO3 perovskite,
which is 3% denser than MgO rocksalt plus Si02 rutile,
to have a velocity 6% faster, which is consistent with
our estimates above.
176

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