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Crystallization kinetics of some Ge-Sb-Se glasses
293
Thermchimica Acta, 133 (1988) 293-298 Elsevier Science Publishers B.V., Amsterdam
CRYSTALLIZATION
KINETICS
S. BORDAd,
CLAVAGUERA-MORd
M.T.
OF
SOME
,
Ge-Sb-Se
Glasses
and Ii. CLAVAGUERS
1 Departament
de Ffsica, Facultat de CiBncies, Universitat Autanoma de Barcelona, 08193-Bellaterra, Spain. i Constituents de la Hatsria, Facultad 2 Departament d'Estructura Spain. de Ffsica, Universitat de Barcelona, 08028-Barcelona,
ABSTRACT
The crystallization investigated ential
scanning
results meqts
by
means
both
following
Some
diffraction.
energy
Arrhenius
data.
The values
increase
the
(81
at the
selenium
kind of compensation
(4xldB).
crystallization
experikinetic
of Sb$e3
fit
with Sb content,
from
trend
ex-
factor
of
lxlCFb to
1x10 l6
exponent
ranges
against
composition.
that may be attributed
in most
to
acti-
for the effective
time
occurs
rate
with a
the best
The kinetic
any clear
effect
heating
The pre-exponential same
differ-
same set of
gives
229 kJ/mol
kJ/mol).
increases
for pure
obtained
was
The calorimetric
equation
behaviour
from 75 to
1.2. and 2.5 without
the primary
with
system
analysis,
and continuous
interpreted
the
the rate constant
between
and X-ray
for isothermal
for pure selenium
except
thermal
The Johnson-Mehl-Avrami-Erofe'ev
the experimental vation
in the Ge-Sb-Se
of alloys
differential
calorimetry
obtained
constant
s-l,
of
were successfully
parameters.
cept
kinetics
to
of the glasses.
IBTRODUCTIOB
Glasses erty
of the Ge-Sb-Se
of being
a consequence, detail
their
Cl]. Further
properties,
Thermal Anaiyis
system
transparenp
density,
have the interesting
to infrared
optical
studies
radiation
prophrties
have
microhardness,
have
been carried
optical
been
on their
heat capacities
0 1988 Elsevier Science Publishers B.V.
studied
in
electrical
and elastic
Proc. 9th ICTA Congress,Jerusakm, Israel, 21-25 Aug. 1988
0040~6031/88/$03.50
prop-
from 2 to 16 pm. As
and
294 dilatometric to
the
phase
kinetic the
properties diagram
studies
ternary
kinetics orimetric
were
PROCEDURE
The
elsewhere
C41.
by
powder
X-ray
(DSC) a DSC
and II
ively.
1 with shown of
the in
DSC and
rate
Elmer
were
figure
of
to
of
T, in continuous
equilibrium
the dx/dt,
on
as
calorimetry using respect-
the
lie
subsystem
given
phase on
of
of
As
Sb2Seg powdered
, x,
fraction,
t,
Fig.
region
the
rug of
time,
In
diagram.
regime) lo-15
a function or
experiments,
checked
was
are
crystallized
given
performed
in
ternary
out
were
equipment,
compositions
carried
determine
heating
the
these (under
were
cal-
paper.
scanning
(DTA)
of
from
samples
compositions
of
region
samples
the
related
crystallization
present
compositions
Their
was
crystallization,
the
Netzsch
429
different
part
analysis
allowed
analysis
prepared.
most
all
forming
studied
Differential
a STA
and of
of
state
been
crystallization
the
air-quenched
the
of
solidification
primary
the
RESULTS
corresponding
this
crystals. sample
AND
glass
been
in
have no
paper
has
reported
thermal
glasses
GeSe2-Sb2Se3,-Se
is
diffraction.
Perkln
Eleven
the
glasses
amorphous
differential
only
however
present
and
details
properties
C31,
but
In the
these
measurements
these
system
reported
of
preparation
All
the
c41.
some
EXPERIMENTAL
The
of
system
of
C21.
and
temperature, in
isothermal
ones.
Fig.
l.- Part of the phase
of the studied Se
sb2Se2
Ge-Sb-Se
system
compositions.
diagram
showing
the
295 The
kinetic
rate
of
behaviour
reaction
given
dx/dt
where s
k(T)
the
is
both
rate
being
constant
The
value
function
of of
were
deduced
both
for
at
from
of
deduced
from
a
value
fixed
the
plot
and
with
2 shows,
glass.
The
as
in Table
the
E
effecttive and
with
activation
f(x)
follows
the
of
the
logarithmic
of
x.
The
lnCkgf(x)l
as
heating
plot
values a
of of
dx/dt
ln(kO)
function
of
conditions
by
as
a
and
n
-ln
of
the
the
ln(dx/dt)
plot
of
example, obtained
factor,
kg,
+ E/RT
lnCf(x)l
such
a
for
the
and
the
as
plot
a
function
for
the
activation
kinetic
of
Gei
-ln(l-x).
SSb17
energy,
exponent,
n,
SSe75 the
E, are
given
1.
DISCUSSION
AND
shown
in
effective content
k(T)=kO,exp(-E/RT)
temperature,
continuous
=
an
values
pre-exponential
As
form
C51
comparison
Fig.
a
equatlon-
ln[kgf(x)l
and
taking
= n(l-x)C-ln(l-x)l(n-l)in
isothermal
expression
the
qnd
independent
E was l/T
of
factor
Johnson-Mehl-Avraml-Erofet-ev
f(x)
explained
f(x)
pre-exponential
energy,
was
by
= k(T)
the
crystallization
upon
COACLUSIONS
Table
1,
activation whereas
composition.
the
161.
Fig.
linear
relationship
the
energy kinetic
Therefore,
effect
both
increase
between
is
the
the
plot
both
with shows
exponent
there
3 shows
pre-exponential
of
factor increasing
no
clear
possibility
of
E
quantities
and
versus in
ln
antimony
trend a
of
the
against
compensation There the
is
glasses.
a
296
* IS0 ; 1.25
22
h
K[min
- ::; +10.0
+
2 44 2
-2
Fig.
2.-
composition
21
201 0
0.5
Plot of
ln[kOf(x)l
1.0
Ge7.Sb17.sSe75.
Full
1.5
vs.
-9.n (1-x)
ln(l-x)
for
line is the plot
the sample
with
for n=1.12
250 2 P a w
200
40
30 fdko
Fig.
3.- Compensation
in the GeSe2-Sb2Se3-Se
plot system.
for the
(s-~)
1
crystallization
of
glasses
297 Table
1 ,- Kinetic
Sample Ge
parameters
composition
:
Sb
0
:
0
2.5
of the samples
3
Se
n
ln
kJ/mol
100
kg in 5-1
81s
2.51tO.l
19.7+0.5
90
74
2.2
14.0
5
10
85
107
1.6
19.6
5
15
80
122
1.5
23.5
7.5
17.5
75
123
1.2
22.2
10
20
70
166
1.5
30.2
11.25
21.25
67.5
187
1.2
34.2
15.79
21.05
63.1%
189
1.4
28.5
14.1
23.08
62.82
227
1.3
37.4
12.5
25
62.5
208
1.9
34.0
28.57
81.9
208
1.9
35.8
9.53
7.5
The discrepancies composition
near
occur the
for
binary
pure
eutectic,
system.
As most of the remaining
region
of
equlllbrium
primary condition,
we conclude
reflects
the fact that
Sb2.Se3
in
alloy
E,
glasses
and of
Sb2Se3
that probably
the first
glasses the
crystal, the
crystallization
with
a
GeSeg-SbpSeg
have a composition
of
crystallization
effect
these
selenium
ta
the under
compenaatiqn product
iS
glasses.
ACKBOWLEDGBMEBTS
This work cientifica
was
suported
y T&cnica"
by the (CAICYT)
"Comislbn project
Asesora
?lo 759/84.
de
InvestigaciBn
298 REFERENCES
1 J.A.
Savage,
P.J.
Webber
and
A.M.
Pitt,
J.
Mater.
Sci.
13
(1978)
859. 2 A.
Giridhar,
Solids
31
(1983)
423;
3 S.
(1980)
Bordas,
Acta 4 S.
P.S.L.
52
Mora,
ibid.8
Q
&
(1984)
233.
Clavaguera-Mora
Surifiach,
J.
Non-Cryst. Galwey,
S.
Mahadevan,
(1981)
29,
and
Legendre,
B.
J.
301,
365;
Non-Cryst. Ibid.
57
Thermochlmlca
161. Casas-VBzquez,
Thermochlmlca
5 S.
6 A.K.
J.
and
105;
ibid., M.T.
(1982)
Bordas,
Narasimham
M.D.
Acta Barb,
Solids Adv.
53
Catal.
N. 22
(1979)
M.T.
209.
(1977)
and
M.T.
Clavaguera-
387.
Clavaguera-Mora
(1983) 23
Clavaguera
247.
and
N.
Clavaguera,
Thermchimica Acta, 133 (1988) 293-298 Elsevier Science Publishers B.V., Amsterdam
CRYSTALLIZATION
KINETICS
S. BORDAd,
CLAVAGUERA-MORd
M.T.
OF
SOME
,
Ge-Sb-Se
Glasses
and Ii. CLAVAGUERS
1 Departament
de Ffsica, Facultat de CiBncies, Universitat Autanoma de Barcelona, 08193-Bellaterra, Spain. i Constituents de la Hatsria, Facultad 2 Departament d'Estructura Spain. de Ffsica, Universitat de Barcelona, 08028-Barcelona,
ABSTRACT
The crystallization investigated ential
scanning
results meqts
by
means
both
following
Some
diffraction.
energy
Arrhenius
data.
The values
increase
the
(81
at the
selenium
kind of compensation
(4xldB).
crystallization
experikinetic
of Sb$e3
fit
with Sb content,
from
trend
ex-
factor
of
lxlCFb to
1x10 l6
exponent
ranges
against
composition.
that may be attributed
in most
to
acti-
for the effective
time
occurs
rate
with a
the best
The kinetic
any clear
effect
heating
The pre-exponential same
differ-
same set of
gives
229 kJ/mol
kJ/mol).
increases
for pure
obtained
was
The calorimetric
equation
behaviour
from 75 to
1.2. and 2.5 without
the primary
with
system
analysis,
and continuous
interpreted
the
the rate constant
between
and X-ray
for isothermal
for pure selenium
except
thermal
The Johnson-Mehl-Avrami-Erofe'ev
the experimental vation
in the Ge-Sb-Se
of alloys
differential
calorimetry
obtained
constant
s-l,
of
were successfully
parameters.
cept
kinetics
to
of the glasses.
IBTRODUCTIOB
Glasses erty
of the Ge-Sb-Se
of being
a consequence, detail
their
Cl]. Further
properties,
Thermal Anaiyis
system
transparenp
density,
have the interesting
to infrared
optical
studies
radiation
prophrties
have
microhardness,
have
been carried
optical
been
on their
heat capacities
0 1988 Elsevier Science Publishers B.V.
studied
in
electrical
and elastic
Proc. 9th ICTA Congress,Jerusakm, Israel, 21-25 Aug. 1988
0040~6031/88/$03.50
prop-
from 2 to 16 pm. As
and
294 dilatometric to
the
phase
kinetic the
properties diagram
studies
ternary
kinetics orimetric
were
PROCEDURE
The
elsewhere
C41.
by
powder
X-ray
(DSC) a DSC
and II
ively.
1 with shown of
the in
DSC and
rate
Elmer
were
figure
of
to
of
T, in continuous
equilibrium
the dx/dt,
on
as
calorimetry using respect-
the
lie
subsystem
given
phase on
of
of
As
Sb2Seg powdered
, x,
fraction,
t,
Fig.
region
the
rug of
time,
In
diagram.
regime) lo-15
a function or
experiments,
checked
was
are
crystallized
given
performed
in
ternary
out
were
equipment,
compositions
carried
determine
heating
the
these (under
were
cal-
paper.
scanning
(DTA)
of
from
samples
compositions
of
region
samples
the
related
crystallization
present
compositions
Their
was
crystallization,
the
Netzsch
429
different
part
analysis
allowed
analysis
prepared.
most
all
forming
studied
Differential
a STA
and of
of
state
been
crystallization
the
air-quenched
the
of
solidification
primary
the
RESULTS
corresponding
this
crystals. sample
AND
glass
been
in
have no
paper
has
reported
thermal
glasses
GeSe2-Sb2Se3,-Se
is
diffraction.
Perkln
Eleven
the
glasses
amorphous
differential
only
however
present
and
details
properties
C31,
but
In the
these
measurements
these
system
reported
of
preparation
All
the
c41.
some
EXPERIMENTAL
The
of
system
of
C21.
and
temperature, in
isothermal
ones.
Fig.
l.- Part of the phase
of the studied Se
sb2Se2
Ge-Sb-Se
system
compositions.
diagram
showing
the
295 The
kinetic
rate
of
behaviour
reaction
given
dx/dt
where s
k(T)
the
is
both
rate
being
constant
The
value
function
of of
were
deduced
both
for
at
from
of
deduced
from
a
value
fixed
the
plot
and
with
2 shows,
glass.
The
as
in Table
the
E
effecttive and
with
activation
f(x)
follows
the
of
the
logarithmic
of
x.
The
lnCkgf(x)l
as
heating
plot
values a
of of
dx/dt
ln(kO)
function
of
conditions
by
as
a
and
n
-ln
of
the
the
ln(dx/dt)
plot
of
example, obtained
factor,
kg,
+ E/RT
lnCf(x)l
such
a
for
the
and
the
as
plot
a
function
for
the
activation
kinetic
of
Gei
-ln(l-x).
SSb17
energy,
exponent,
n,
SSe75 the
E, are
given
1.
DISCUSSION
AND
shown
in
effective content
k(T)=kO,exp(-E/RT)
temperature,
continuous
=
an
values
pre-exponential
As
form
C51
comparison
Fig.
a
equatlon-
ln[kgf(x)l
and
taking
= n(l-x)C-ln(l-x)l(n-l)in
isothermal
expression
the
qnd
independent
E was l/T
of
factor
Johnson-Mehl-Avraml-Erofet-ev
f(x)
explained
f(x)
pre-exponential
energy,
was
by
= k(T)
the
crystallization
upon
COACLUSIONS
Table
1,
activation whereas
composition.
the
161.
Fig.
linear
relationship
the
energy kinetic
Therefore,
effect
both
increase
between
is
the
the
plot
both
with shows
exponent
there
3 shows
pre-exponential
of
factor increasing
no
clear
possibility
of
E
quantities
and
versus in
ln
antimony
trend a
of
the
against
compensation There the
is
glasses.
a
296
* IS0 ; 1.25
22
h
K[min
- ::; +10.0
+
2 44 2
-2
Fig.
2.-
composition
21
201 0
0.5
Plot of
ln[kOf(x)l
1.0
Ge7.Sb17.sSe75.
Full
1.5
vs.
-9.n (1-x)
ln(l-x)
for
line is the plot
the sample
with
for n=1.12
250 2 P a w
200
40
30 fdko
Fig.
3.- Compensation
in the GeSe2-Sb2Se3-Se
plot system.
for the
(s-~)
1
crystallization
of
glasses
297 Table
1 ,- Kinetic
Sample Ge
parameters
composition
:
Sb
0
:
0
2.5
of the samples
3
Se
n
ln
kJ/mol
100
kg in 5-1
81s
2.51tO.l
19.7+0.5
90
74
2.2
14.0
5
10
85
107
1.6
19.6
5
15
80
122
1.5
23.5
7.5
17.5
75
123
1.2
22.2
10
20
70
166
1.5
30.2
11.25
21.25
67.5
187
1.2
34.2
15.79
21.05
63.1%
189
1.4
28.5
14.1
23.08
62.82
227
1.3
37.4
12.5
25
62.5
208
1.9
34.0
28.57
81.9
208
1.9
35.8
9.53
7.5
The discrepancies composition
near
occur the
for
binary
pure
eutectic,
system.
As most of the remaining
region
of
equlllbrium
primary condition,
we conclude
reflects
the fact that
Sb2.Se3
in
alloy
E,
glasses
and of
Sb2Se3
that probably
the first
glasses the
crystal, the
crystallization
with
a
GeSeg-SbpSeg
have a composition
of
crystallization
effect
these
selenium
ta
the under
compenaatiqn product
iS
glasses.
ACKBOWLEDGBMEBTS
This work cientifica
was
suported
y T&cnica"
by the (CAICYT)
"Comislbn project
Asesora
?lo 759/84.
de
InvestigaciBn
298 REFERENCES
1 J.A.
Savage,
P.J.
Webber
and
A.M.
Pitt,
J.
Mater.
Sci.
13
(1978)
859. 2 A.
Giridhar,
Solids
31
(1983)
423;
3 S.
(1980)
Bordas,
Acta 4 S.
P.S.L.
52
Mora,
ibid.8
Q
&
(1984)
233.
Clavaguera-Mora
Surifiach,
J.
Non-Cryst. Galwey,
S.
Mahadevan,
(1981)
29,
and
Legendre,
B.
J.
301,
365;
Non-Cryst. Ibid.
57
Thermochlmlca
161. Casas-VBzquez,
Thermochlmlca
5 S.
6 A.K.
J.
and
105;
ibid., M.T.
(1982)
Bordas,
Narasimham
M.D.
Acta Barb,
Solids Adv.
53
Catal.
N. 22
(1979)
M.T.
209.
(1977)
and
M.T.
Clavaguera-
387.
Clavaguera-Mora
(1983) 23
Clavaguera
247.
and
N.
Clavaguera,