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GLASSES
ABSTRACT
Phase transformgtionshave been studied in glasses related in composition to
Li20-MgO-Si02 (930 C) eutectic glass modified by A1203/Li20 replacement on a
cation per cation basis. Crystallization processes and changes in the solid
solutions of the mineral phases developed during the controlled heating of the
glasses have been followed using X-ray and microscopic techniques.
Solid solutions of lithia aluminosilicate phases (B-eucryptiteand/or Bspodumene s.s.) are the essential minerals that crystallize in glasses through
most of the heat treatment applied. Lithium metasilicate, disilicate, clinoenstatite and cordierite are also encountered.
B-eucryptite S.S. is formed in early stage of crystallizationof the glass
which transforms into B-spodumene S.S. at higher temperature (800 C). However,
in some cases, it persists at temperatures as high as 10000 C.
Metastable B-eucryptite-B-quartzS.S. can accomodate considerable amounts of
Mg2+ and A13+ ions in its lattice especially at lower temperature. At higher
temperature for long duration, a redistribution of the elements takes place, and
the cordierite phase then developed.
INTRODUCTION
The synthesis of crystalline species of low thermal expansion has long been an
important fact of ceramic technology D-3.
When glasses are crystallized by thermal treatment, they frequently pass
through a series of crystalline states before reaching an equilibrium[4,5].
These early 'protocrystalline'states often reflect to some degree, the general
disorder of the original glass.
Solid solutions structurally analogous to the high-temperature form of quartz,
B-quartz, are perhaps the best examples of such protocrystallineforms. These
are easily formed from a great variety of aluminosilicateglass compositions.
Perhaps their most significant property is very low thermal expansion [6,7].
0254-0584/84/$3.00
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146
In
The glass
ceramics obtained have good thermal shock resistance, are more refractory than
the original glasses, and have much higher mechanical strength.
The crystallizationof glasses in the magnesia-alumina-silicasystem has also
produced glass ceramics with medium to low thermal expansion coefficients, good
electrical insulation and high mechanical strength. These properties have been
attributed to the presence of cordierite LlO] (2MgO-2A1203-5Si02)as the principal phase.
The formation of ceramic materials containing such solid solution phases which
have been derived from glasses of Limo-MgO-Al203-SiO2composition is the subject
of this paper.
EXPERIMENTAL
Batch composition
The batch compositions were prepared based on the Li20-MgO-SiO2 eutectic
(930' C) glass, in which 25, 50, 60 and 75 % of the Li20 content was replaced by
A1203 on a cation per cation basis. The chemical compositions of the glasses
studied are given in Table I.
1
2
3
4
5
Oxides (mole %)
Li20
23.12
17.34
11.56
9.25
5.78
Oxides (wt %)
Al203
MgO
Si02
Li20
A1203
MgC
Si02
13.28
13.28
13.28
13.28
13.28
63.60
63.60
63.60
63.60
63.60
13.70
9.49
5.88
4.57
2.75
10.79
20.05
23.39
28.08
10.60
9.80
9.10
8.85
8.50
75.70
69.92
63.97
63.19
60.67
5.78
11.56
13.87
17.34
The batch components were prepared from materials of Analar and Reagent grade
quality in the form of pulverized powders. Silica was introduced in the form of
Abu Darag (from Egypt) white sand of 99.4 wt % SiO2. Li20 and MgO were introduced in the form of their respective carbonates, while aluminium oxide was introduced in the form of calcined alumina.
147
Glass preparation
The glass batches, after being accurately weighed and well mixed, were melted
in platinum 2% Rh crucibles in an electric furnace with Sic heating element at
temperatures ranging from 1300 to 1500' C for 3 to 5 h, depending on the composition of the batch. Melting was continued until a clear homogeneous glass was
obtained. This was achieved by swirling the melt several times 30 min apart.
The melts were normally cast onto a stainless steel marver into steel moulds in
the form of discs. The resultant glasses were properly annealed in a muffle
furnace to give strain-free samples.
Heat-treatment process
In accordance with the DTA data, the glass samples were subjected to two types
of heat-treatment schedules as follows :
a
One-step heat treatment in which the glasses were soaked at a definite tem-
Two-step heat treatment in which the glasses were soaked at 750 or 850' C for
5 h and then at 950 or 1050' C for 3 h, respectively, namely 1st and 2nd twostep schedules. In the high A1203-containingglass, a third step schedule
was also applied in which the soaking time of the second temperature step
(1050' C) was extended to 15 h.
X-ray analysis
The X-ray diffraction technique was used to identify the mineral phases and
their solid solutions developed, using a Siemens X-ray diffractometer type D-500
adopting a Ni filter and Cu radiation.
Optical microscopy
Thin sections were prepared from the specimens obtained after heat-treatment
to examine optically the mineralogical constitution as well as the textures
formed, using a polarizing Carl-Zeiss research microscope.
148
RESULTS
Differential thermal analysis
Two glasses, namely 3 and 4 (with 50 and 60% Al 0 /Li20 substitution, res23
pectively), were taken into consideration to study the thermal behaviour of
A1203-containing glasses by the DTA technique. The differential thermogram of
G3 (Fig. 1) showed an endothermic effect at about 700' C, probably corresponding
to the precrystallizationprocesses in the glass. This is followed by a strong
exothermic effect at about 800' C and a weak exothermic peak at 95Oo C.
The DTA
Crystallization process
In general, the crystallization of Al203-containingglasses was more or less
a sluggish process as compared with the A1203-free glass. The replacement of
Li20 by A1203 greatly increases the temperature at Fjhichthe crystallization
starts. The eutectic glass 1 began to crystallize at 650' C and was converted
into a holocrystallinemass at 850' C; however, the latter temperature is just
enough for starting the crystallization in glass 5 (with 75% A1203).
149
developed as a major
phase (major lines 4.52, 3.47, 3.86, 2.59, 1.87, 1.63 8) with some clinoenstatite
as a minor phase, whereas glass 5 (with 75% A1203 substitution, pattern Vl
crystallized only into a B-eucryptite s.s. phase. These findings should be
compared with those obtained from A1203-free glass (i.e., glass 1, pattern I),
where lithium disilicate, clinoenstatite and alpha-quartz were only formed.
The formation of B-eucryptite and/or B-spodumene solid solutions was found to
be dependent mainly on the crystallization parameters used as well as the A1203
content in the glasses.
Fig. 3 clearly indicates that glass 3 (pattern I) yielded a B-eucryptite S.S.
phase at 800' C for 3 h, whereas this phase was developed from glass 4 (with
high A1203 content pattern III at temperatures of 900' C using the same soaking
time. However, on prolonged heating (&,
loped from glass 3, whereas B-eucryptite still persisted in glasses 4 & 5, even
after treatment at 900' C for 15 h (Fig. 4). A magnesium silicate phase
(clinoenstatite)was also developed as a minor constituent.
Fig. 2,
glasses,
X-ray diffraction
patterns of eutectic an6 AL 0 -containing
erystafllzed
at 15Oo C for 5 h and at 95Oo C ?o$ 3 h.
T%ePefore,
may correspond
enstatfte,
the
exbthermic
transfwmation
given
effect
to the simultaneous
of B-eucryptite
by
glass
crystallization
effect
S.S.
into
3 jFig.
11
eutectic
at about &IO C
of B-eucryptite
and cfino-
to the
151
Glass L ,at
900C.3h.
5:
68
80
72
6L
56
_i
LB
LO
32
2L
16
28
Fig.
ized
3. X-ray
according
diffraction
to one-step
patterns
regime.
of
A1203-containing
eutectic
glasses
crystall-
.
c- ss
p - CC
f3 - Sped -ss
Clinoenst
I-Glass
3.8X
15h.
$
III-Glass
Fig.
4.
allized
5.900 15h
.+ak
X-ray diffraction
patterns
of
according
to one-step
regime.
A1203-containing
eutectic
glasses,
cryst-
152
The B-eucryptite - B-spodumene transformation in glasses 4 and 5 was most
clearly illustrated when the crystallization took place at high temperatures
and/or prolonged heating. X-ray examination, Fig. 5, indicated that glass 4
crystallized through the 2nd two-step schedule (pattern I) yield B-eucryptite
S.S. together with a little amount of B-spodumene S.S. On prolonged heating,
(i.e., 3rd two-step schedule) only B-spodumene S.S. was developed as the lithia
aluminosilicate phase among the crystallizationproducts of glass 4 (pattern II).
p-euc-ss .
+ Clinoenst.
I-Glass
/3-sped-ss
-$pwk
x Cord.
F
Q
1050C 3h I.
II-Glass
4 (850 C 5h-
t-
-&ak
2
4(850C5h-1050C15hI.
IlI-Glas~5(8!Xl~C
5h-105OC
3h).
+peak
B
A
Speak
15h). 2
153
Fig. 7., G
(800' C 3 h) . Interlocked
spherulite growth s of
B-eucryptl .2 e s.s and clinoenstatite
crystals with some gla ssy
matrix in the interstices.
C.N.
X 75
155
Fig. lo., G4 (850' C 5 h - 1050' C 15 h) Volume crystallizationof a(ggregates of B-spodumene s.s. with some tiny clinoenstatite crystals. C. N.
x 75
156
Accordingly, it therefore follows, from the DTA data of glass 4 (Fig. l),
that the first exothermic effect at about 860' C may correspond to B-eucryptite
and clinoenstatite formation. The second exothermic effect at 980' C may correspond to the temperature at which the B-eucryptite - B-spodumene transformation
took place.
Glass 5 crystallized through the 2nd two-step schedule into a B-eucryptite
solid solution (Fig, 5, pattern III), whereas, on prolonged heating (3rd twostep schedule), B-spodumene S.S. was developed in a little amount together with
B-eucryptite S.S. among the crystallizationproducts of this glass (pattern IV).
It should be mentioned that clinoenstatitewas detected as a minor constituent among the crystallizationproducts of all A1203-containingglasses crystallized under this condition. Meanwhile, cordierite (major lines 8.45, 3.18,
3.14, 3.03 8), was formed only among the crystallizationproducts of glass 5,
especially after heat-treatment through the 3rd two-step schedule (Fig. 5,
pattern IV).
Microscopic examination of thin sections of the crystallized samples confirmed
all the above mentioned results (Figs. 6-11).
DISCUSSION
It is well known that alumina as well as silica are effective in increasing
the viscosity of the glass due to the formation of polymorph units, AlO
Si04 groups LllJ.
and
under investigation resulted in highly viscous melts especially in those containing high A1203 content.
The crystallizationof A1203-containingglasses especially glasses containing
A1203/Li20 higher than unity, showed a sluggish process as compared with that of
A1203-free glass. These glasses did not attain the holocrystalline state below
lOOO-1050' C, while Cl (free of A1203) was holocrystallinealmost free of residual glass at 800;850' C, the temperatures at which G4 and G5 (with high A1203
content) began to crystallize. The sluggish crystallizationnature of the high
alumina containing glasses under investigation may be explained on the basis that
when A1203 is added to the lithia-silica, the non-bridging oxygens originally
associated with the Li+ ions increase the coordination numbers of the A13+ ion
from three-fold to four-fold coordination. The Li+ ions deprived of their
polarizable oxygens are no longer capable of developing a two-phase separation,
and thus the glass looses its ability to crystallize uniformly L123.
On the
other hand, the replacement of Li20 by Al203 causes an increase in the viscosity
of resultant glasses, which is increased by introducing more A1203 in the glasss
composition. Therefore, it seems to be that the increase of viscosity hinders
the diffusion of the different ions and ionic complexes and consequently
decreases the rate of crystal growth. Although A1203 is detrimental to uniform
157
At
158
No magnesiumaluminosilicate
phase was detectedamong the crystallization
productsof glass 4, even after prolongedheatingat 1050' C. However,this
compoundwas detectableunder such conditionas a minor constituent
only in
glass 5 (withA32031Li20: 3) in the form of a cordieritephase (Mg2A14Si5018f.
Table II. NormativeCalculationof Samples1, 2 and 3.
NO.
Mole of Li20
substituted
by A12Q3
1
2
3
25
50
Glass
Li20/A1203
% of normativemolecules
ratio
LiAlSi206
Li2Si205
MgSiO3
SiO2
3
1
37.63
75.10
75.16
37.53
-
21.56
21.56
21.50
3.28
3.28
3.40
159
as was previously mentioned, replace the SiO4 tetrahedra, and electrical neutrality is preserved by means of interstitial octahedrally coordinated stuffing ions
+
2+
such as Li and Mg .
In the present work, it was observed that the amount of MgSiO3 formed was decreased in the higher Al 0 -containing glasses. This may be attributed to the
23
capability of B-eucryptite to take Al3+ ions in its lattice, which is accompanied
2+
by incorporation of Mg
Ions to preserve the electrical neutrality. Therefore,
the higher the A1203 content in the glass, the smaller is the MgSi03 phase formed
during crystallization.
It was assumed on the basis of petrochemical calculation of normative mineral
molecules, that the excess A1203 (over Li20) after the formation of the lithiumbearing mineral (B-spodumene)was alloted with MgO to form MgA1204. If there is
no residual free silica, MgA1204 can incorporate in the B-spodumene lattice, but
in the presence of an appreciable amount of free silica, after saturation of the
B-spodumene solid solution, the cordierite phase (Mg2A14Si5018)separated out
especially at high temperature for long duration, according to the following
schematic equation.
Mg2A14Si5018
spine1
cordierite
silica
Table III. The Amount of Silica (in atoms) Required for Spodumene Formation and
the Residual Free Silica Remaining after Saturation of the Other Minerals formed
in Glasses 4 & 5.
Glass
No.
A1203/Li20
molar ratio
Total
spodumene
Silica of
spodumene
MgA1204
MgSi03
Free
silica
4
5
1.5
3.0
1224
736
612
368
228
549
286
54
297
615
Table IIIshows that the amount of free silica in glass 4 is too small to
satisfy the formation of B-spodumene S.S. This phase can take an equal amount
of its silica content in its structure (i.e., Li20:A1203:8Si02). In other words,
the remaining free silica can be wholly incorporated in the B-spodumene lattice.
The MgA1204 molecules seemed to be accomodated in this solid solution forming a
complex aluminosilicate S.S. phase of the probable chemical formula,
160
Therefore, cordierite phase 2Mg@.2A1203.5Si02cannot be formed from such
glass composition. This agrees fairly well with the X-ray data of the crystalline products of this glass.
In glass 5, on the other hand, Table III shows that the residual amount of
silica is greater than the maximum permissible value for B-spodumene S.S. formation. The residual free silica after saturation of B-spodumene S.S. can then
combine with MgA1204 molecules to form cordierite.
Actually, the X-ray analysis revealed that, for glass 5, the B-eucryptite B-quartz solid solution of the probable chemical formula 0.33 Li20 - 0.67 MgO 1.0 A1203 - 3.57 Si02 was developed after heat treatment at 1050' C for 3 h.
However, on prolonged heating (15 h) a redistribution of the elements took place
and the cordierite phase could be formed[8,10].
REFERENCES
F.A. Hummel, J. Am. Ceram. Sot. 33 (3) (1950) 102.
F.A. Hummel, Ibid. 34 (8) (1951) 235.
F.A. Hummel, Ibid. 35 (3) (1952) 64.
R. Roy, Symposium on nucleation and crystallizationof glasses and melts,
Edited by M.K. Reser, Geraldine Smith and Herbert Insley, Am. Ceram. SOC.,
Inc., Columbus, Ohio, 1962, p. 39.
S.B. Holmquist, 2. Krist. 118 (5-6) (1963) 477.
R. Roy, Z. Krist. 111 (3) (1959) 185.
G.H. Beal, B.R. Karstetter and H.L. Rittler, J. Am. Ceram. Sot. 50 (4)
(1967) 181.
8
SOC.
35 (1952) 322
COnsUltantS