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Phase relations and glass formation in the systems CaSGa2S3GeS2 and SrSGa2S3GeS2
Phase relations
and glass formation in the systems CaS-Ga,S,-GeS, and SrS-Gals,-GeS,’ b!. F!:?!x~c!fT. c??.Schmi~l! / ,,,r,r ,,,,, rr110 !I,,,r\,r,lr
2. Experimental
1. Introduction Chalcogcnidc plassc~ have hccn studied cuIcn\ively during the last IWO dccade~ 1 I ] One ol the prommcnt glass lorming invcstigatcd
with
quasi-binary started GcS,
chalcogcnidcs rcspcct
and -ternary
an investigation whcrc
paper
ahich
systems
y&. The lirsl
has hccn
WC present
ol’ our
hcen
In many ago
systems. Some years 01 Ihc
lo the hcsl
as
ha\
IO glass formatton
M is one of Ihc alhalinc
Ca. Sr or Ba which. not hecn trca~cd Ba system.
is GcS,.
earth
clcmcnts
knowlcdpc.
recently
the results of our
the quasi-hinary
research
Ga,S,-GeS, Guittard 55 mol% formation
of Ihc
ltllc
lircd
on Ihc
has been studied by Loircdu-Lorac’h Ga,S,. has
glass formation
For the other horder been
systems
crystalline
Ca,GeS,
161, SrGa,S,
reported
the sample\ iscd and
so
[4] and Sr,GeS,
hut
C’aGa,S,
in
n92.%3xNYfd$l.5.(n) 0 IY?Hi P/I SoYZS-X3XX(Yh)O2434-h
IW
with
using Cu
KU,
these
brated
(4.51.
5.4054 A)
60th
were
parts
I IOU K
The
quenched
hy
spectra
procedure
and while
powder
IV
camera
were cali-
((I = 4.9136. refined
c = by a
[IO].
were recorded
of 4 cm-‘.
X-ray
Guinier photographs
o-quartz
were
slowly in
IO cool
and the unit cell dimensions
least-squares
which
time the samples
were
investigated
with
trophotometcr Bruker mulled in NUJOI and resolutmn
equal
an Enraf-Nonius
internally
the
As a first step
I IC4) K for 1 week.
Ihc reaction
K were allowed
radiation.
by re-
from
from the elements
BI 1050 K. then homogen-
three
and
at 900
method\
FIR ‘Dedic.a!d birthday.
at
and
[7] are formed.
into
WI) K for 2 weeks. After tempsred
carbonates (prepared
silica ampoulcs.
were prcrcacted
dotdcd
0 to
systems no glass
far:
compounds
from
Ga,S: (prcparcd
I3IH) K for 5 days.
a(
Ihc o:cn. The sampl.z\
systems.
IX]).
K) m cvacuatcd
Ihosc rcactcd
cdgcs
131 who ohserved
I IlW)
Ihc corrcspondin~
tl,S
[I)]) and GcS,
the
121. In this
Irom
with
had
systems with M = Ca and Sr. From
(prepared action clcmcnI\ at
MS-Ga,S,-
part of this work.
puhlishcd
\f u
For the m\c\tigaIion of Ihc phase diagram. samples \verc prepared from Ihc binary sullidcs CaS and SrS
with
the Fourier
spec-
IFS 114V. The samples were the spectra recorded with a
new compound ohtaincd. pound with
The
with
an unknown
X-ray
diffraction
can hc indcxcd (I = %!S.O(
Attempts
I ) and
has hecn
of this com-
)
cell
c = 602.4( I pm (SW Tahlc I ). to grow single crystals by transport rcaclions
or by crystallization spectrum
structure pattern
on the hasis of a tctragonal
from the melt failed. The infrared
of this compound
Samples
in the G&,-rich
can hc ohlaincd
is shown in Fig. 2. part of the phase diagram
in a glassy state. The
area
in which
glasses arc fnrmcd is strongly dependent on the temperature at which Ihc samples arc quenched. The fields in which glasses arc formed by quenching at
I
0
I
2
0
II
hltlltlh
2.OSlII
2.oml1
I
s I,400
I.Yh2-l
IYh2h
I
4.~~270
l.Y53l
I I I I I 2 ? 2 I
l.hSl8
I.YX?h I.‘)107 ISI?3 I Xllhl I .79Y7 I .737e I.7li.ii I.71 I2 I.hA2.l I .hSllX
I.h.lSi
I.h3JX
?.wll
‘1
I s.540
l.SSJS
I
3
lslml
I30lh2
I
I
0
3
II
I
I
I
?
3 2
I I
I ,
3
2
I
5 IUXII 4.hl.l’) 4.43 I I 4 13hfl 3 -ill11 ? ‘L?iO ?.XlJI 2 X64, 17117 ? 735Y Zh.113 ?.43.SO 2 3hO.l
4 7
0
II
23124
2 3loll
2
2
2 21.55
2.2150
3
3
,I
2 IX02
2.lXlll,
3
1
2
2 0984
2.09x0
4
2
II
2.ohx3
?.llhW
I
I
I
2 2
I
0
I
I
3
I
0
2
I
JJ3Ill
I.YlYh
4.1371)
h
I.XI4ll
3 4IlYO
IO
Ixllfls
2 Y310
1.7w2
2.874ll
1.7370
?.XMO
I717h
2 74.10
7
I.7112
2.73hll
II 7
1.6X27
2.h320 243x,
IO
I 2
I.JYh2
I.JYhS
I I
I
I.4921
I.JYI.1
I
14744
I.47.50
1
GeS,
Galhum
GmhH.
of pure galhum.
Schwendorl.
and glass formation in the systems CaS-Ga,S,-GeS, and SrS-Gals,-GeS,’ b!. F!:?!x~c!fT. c??.Schmi~l! / ,,,r,r ,,,,, rr110 !I,,,r\,r,lr
2. Experimental
1. Introduction Chalcogcnidc plassc~ have hccn studied cuIcn\ively during the last IWO dccade~ 1 I ] One ol the prommcnt glass lorming invcstigatcd
with
quasi-binary started GcS,
chalcogcnidcs rcspcct
and -ternary
an investigation whcrc
paper
ahich
systems
y&. The lirsl
has hccn
WC present
ol’ our
hcen
In many ago
systems. Some years 01 Ihc
lo the hcsl
as
ha\
IO glass formatton
M is one of Ihc alhalinc
Ca. Sr or Ba which. not hecn trca~cd Ba system.
is GcS,.
earth
clcmcnts
knowlcdpc.
recently
the results of our
the quasi-hinary
research
Ga,S,-GeS, Guittard 55 mol% formation
of Ihc
ltllc
lircd
on Ihc
has been studied by Loircdu-Lorac’h Ga,S,. has
glass formation
For the other horder been
systems
crystalline
Ca,GeS,
161, SrGa,S,
reported
the sample\ iscd and
so
[4] and Sr,GeS,
hut
C’aGa,S,
in
n92.%3xNYfd$l.5.(n) 0 IY?Hi P/I SoYZS-X3XX(Yh)O2434-h
IW
with
using Cu
KU,
these
brated
(4.51.
5.4054 A)
60th
were
parts
I IOU K
The
quenched
hy
spectra
procedure
and while
powder
IV
camera
were cali-
((I = 4.9136. refined
c = by a
[IO].
were recorded
of 4 cm-‘.
X-ray
Guinier photographs
o-quartz
were
slowly in
IO cool
and the unit cell dimensions
least-squares
which
time the samples
were
investigated
with
trophotometcr Bruker mulled in NUJOI and resolutmn
equal
an Enraf-Nonius
internally
the
As a first step
I IC4) K for 1 week.
Ihc reaction
K were allowed
radiation.
by re-
from
from the elements
BI 1050 K. then homogen-
three
and
at 900
method\
FIR ‘Dedic.a!d birthday.
at
and
[7] are formed.
into
WI) K for 2 weeks. After tempsred
carbonates (prepared
silica ampoulcs.
were prcrcacted
dotdcd
0 to
systems no glass
far:
compounds
from
Ga,S: (prcparcd
I3IH) K for 5 days.
a(
Ihc o:cn. The sampl.z\
systems.
IX]).
K) m cvacuatcd
Ihosc rcactcd
cdgcs
131 who ohserved
I IlW)
Ihc corrcspondin~
tl,S
[I)]) and GcS,
the
121. In this
Irom
with
had
systems with M = Ca and Sr. From
(prepared action clcmcnI\ at
MS-Ga,S,-
part of this work.
puhlishcd
\f u
For the m\c\tigaIion of Ihc phase diagram. samples \verc prepared from Ihc binary sullidcs CaS and SrS
with
the Fourier
spec-
IFS 114V. The samples were the spectra recorded with a
new compound ohtaincd. pound with
The
with
an unknown
X-ray
diffraction
can hc indcxcd (I = %!S.O(
Attempts
I ) and
has hecn
of this com-
)
cell
c = 602.4( I pm (SW Tahlc I ). to grow single crystals by transport rcaclions
or by crystallization spectrum
structure pattern
on the hasis of a tctragonal
from the melt failed. The infrared
of this compound
Samples
in the G&,-rich
can hc ohlaincd
is shown in Fig. 2. part of the phase diagram
in a glassy state. The
area
in which
glasses arc fnrmcd is strongly dependent on the temperature at which Ihc samples arc quenched. The fields in which glasses arc formed by quenching at
I
0
I
2
0
II
hltlltlh
2.OSlII
2.oml1
I
s I,400
I.Yh2-l
IYh2h
I
4.~~270
l.Y53l
I I I I I 2 ? 2 I
l.hSl8
I.YX?h I.‘)107 ISI?3 I Xllhl I .79Y7 I .737e I.7li.ii I.71 I2 I.hA2.l I .hSllX
I.h.lSi
I.h3JX
?.wll
‘1
I s.540
l.SSJS
I
3
lslml
I30lh2
I
I
0
3
II
I
I
I
?
3 2
I I
I ,
3
2
I
5 IUXII 4.hl.l’) 4.43 I I 4 13hfl 3 -ill11 ? ‘L?iO ?.XlJI 2 X64, 17117 ? 735Y Zh.113 ?.43.SO 2 3hO.l
4 7
0
II
23124
2 3loll
2
2
2 21.55
2.2150
3
3
,I
2 IX02
2.lXlll,
3
1
2
2 0984
2.09x0
4
2
II
2.ohx3
?.llhW
I
I
I
2 2
I
0
I
I
3
I
0
2
I
JJ3Ill
I.YlYh
4.1371)
h
I.XI4ll
3 4IlYO
IO
Ixllfls
2 Y310
1.7w2
2.874ll
1.7370
?.XMO
I717h
2 74.10
7
I.7112
2.73hll
II 7
1.6X27
2.h320 243x,
IO
I 2
I.JYh2
I.JYhS
I I
I
I.4921
I.JYI.1
I
14744
I.47.50
1
GeS,
Galhum
GmhH.
of pure galhum.
Schwendorl.