145

Materials Chemistry and Physics, I1 (1984)145-160

SOLID SOLUTION PHASES FROM THERMALLY CRYSTALLIZED Li20-Mg0-A1203--2

GLASSES

S.M. SALMAN and A.A. OMAR

Glass Research Laboratory, National Research Centre, Dokki, Cairo (Egypt)
S.N. SALAMA
X-Rays Division, Central Services Laboratory, National Research Centre, Dokki,
Cairo (Egypt)
Received 14 February 1984; accepted 11 March 1984

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

0 Elsevier
Sequoia/Printed
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146

Roy [6J reported that the Si02-Li20.Al203.

2SiO2 system formed a complete
series of solid solutions with B-quartz structure. Later, Beal et al. c7J and
Ray et al.L8J reported the formation of such solid solutions in glass ceramics
of the Li20-(MgO)-Al203-Si02system. These solid solutions were designated as
silica-0 by Roy and as B-quartz solid solution by Beal et al.
The two major crystalline phases formed from lithia-alumina-silicaglasses are
tetragonal B-spodumene (Li20-A1203-4Si02)and hexagonal B-eucryptite iLi20-A12032SiO2).

In

the eucryptite-spodumenesystem, each compound is capable of entering

the crystalline lattices of the other in significant amountsc9J.

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.

Table I. Chemical Composition of the Glasses.

Glass
NO.

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.

Differential thermal analysis

The DTA technique was used in the present work to investigate the thermal
behaviour of the glasses. 50 mg of finely divided glass powder, together with a
similar quantity of A1203, were placed in a platinum holder of the DTA apparatus
and it was heated against another platinum holder containing 100 gm A1203 as a
standard material. A uniform rate of heating of 10' C/min. was adopted up to
1000 C in all experiments and a sensitivity of 0.5 mV for differential current
amplification was found suitable. The data obtained from the differential
thermograms are considered as a criterion for determining the heat-treatment
process applied to the glasses investigated.

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

perature ranging from 650 to 1000 C at 50' C intervals for 3-15 h.

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

record of G4 showed an endothermic peak at about 750' C as well as two markedly

strong exo'chermicpeaks at 860 and 980' C.

Fig. 1, DTA curves of some A1203-containingglasses.

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

The crystallization process, in most cases, began as a surface crystallization

with highly glassy matrix which decrease as the temperature was increased.
Applying the two-step heat treatment schedule, volume crystallizationwas obtained, and the glasses converted into strong ceramic material of holocrystalline
mass without deformation, especially after treatment through the 2nd and 3rd
two-step regime. The deformation tendency was greatly decreased in the glasses
by A1203/Li20 replacement. The eutectic glass crystallized with a slight deformation at 950' C, while the A1203-containingglasses showed no deformation after
thermal treatment up to 1050' C.

Phases and solid solutions developed

Mneralogically, the addition of A1203 (instead of Li20) in the glass led to
the formation of lithium-aluminiumsilicate solid solution phases; B-eucryptite
S.S. and/or B-spodumene S.S. This takes place at the expense of the lithium
disilicate phase. The increase of A1203 in the glass led to a corresponding
increase of aluminosilicate and a decrease in the lithium silicate formation. A.
clinoenstatite phase was also formed among the crystallizationproducts of these
glasses.
Inspection of Fig. 2 indicates that glass 2 (with 25% A1203 substitution
pattern II) developed a B-spodumene solid solution (major lines 4.58, 3.88,
3.46, 3.16, 1.87 8) as a major constituent with little amounts of lithium metasilicate, lithium disilicate and clinoenstatite. Glass 3 (with 50% A1203 substitution, pattern III) formed essentially a B-spodumene solid solution with
little amount of clinoenstatite. At higher A1203 content _i.e., glass 4 (with
60% A1203 substitution, pattern IV) B-eucryptites.s was

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 (&,

15 h) the B-spodumene S.S. was cieve-

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

whereas the sxothermic

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-

at about 950 C may be attributed

B-spodumene 8.9.

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

E-Glass 5(850 C Sh-105OC

Speak
15h). 2

Fig. 5. X-ray diffraction patterns of A1203-containingeutectic glasses,

crystallized according to two-step regimes.

153

Fig. 6., G2 (800' C 3 h) .

Fine prismatic B-spodumene
s.s . crystals together with spherulite growths of lithium metasilica .te
crystals and some glassy phase inbetween.
C.N.
X 75

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

Fig. 8., G (75O'C 5h-950'

3 h) Spherulite growths of fine prismatic
B-spodumen2 S.S. and clinoenstatite crystals. C.N. x 75

Fig. 9., G4 (900' C 3 h) Surface prismatic crystallizationof B-eucryptite

S.S. and tiny aggregates of clinoenstatite crystals in the bulk embedded in
some glassy matrix (20-30X 1 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

Fig. Il., G (850' C 5 h - 1050' C 15 h) Heterogeneous grained textsu-e of

fine fibrou2 B-eucryptite s.s and B-spodumene s.s crystals with some tiny aggregates of cordierite and clinoenstatite.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

Therefore, the replacement of Li20 by Al203 in the glasses

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

crystallization of glasses, it is often incorporated as a major constituent in

actual glass ceramics. This improves the glass forming properties as well as
the properties of the corresponding glass ceramics.
The occurrence of the various phases developed was a function of the Al2031
Li20 ratios in the glass and the crystallizationparameters used. At low A1203
content *.,

when Li20 was greater than A1203 (glass 2) , B-spodumene

(LiA1Si206)was developed as a major constituent; clinoenstatite (MgSiOJ),

lithium metasilicate together with lithium disilicate were detected as well.

At

A1203/Li20 equal to unity (glass 3), lithium aluminosilicate (B-eucryptiteor

B-spodumene) and magnesium metasilicate only were detected.
Li20 exhibits a very great affinity to combine with A1203 and Si02 to form
aluminosilicate. In the petrochemical method for the calculation of normative
mineral molecules L13-Jfrom the chemical composition, it is observed that when
A1203 is present it should be first combined with an equivalent amount of Li20
and SiO2 to form lithium aluminium silicate (B-eucryptiteor B-spodumene). If
there is an excess of Li20 over A1203 in molar ratios (as in case of glass 2),
it can then combine with silica to form lithium silicate phases.
The formation of B-spodumene and/or B-eucryptite takes place at the expense
of the lithium silicate phase. Thus, the increase of Al203 content up to 50%
substitution (i.e., A1203/Li20 ratio equal to unity) caused an increase in the
amount of lithia aluminosilicate phases formed and led to a corresponding decrease in the amount of lithium silicate phase (as proved by X-ray examination,
Fig. 2).
Table II shows that a lithium silicate phase was found to be formed in A1203containing glasses, only when the molar ratio Li20/A1203 was greater than unity
(i.e., glass 2).

The lithium silicate phase in this glass was calculated as

Li2Si205 molecules. However, X-ray analysis revealed that lithium metasilicate

(Li2Si03) was detected in appreciable amounts together with a little amount of
lithium disilicate. This may be attributed to the fact that the tendency of Bspodumene, which had been formed in glasses 2 and 3, to form a solid solution
L6-8,143 renders the residual glass to be relatively poor in silica. Therefore,
no free silica is detected among the crystallization products of these two
glasses. The residual glass is then relatively unsaturated, and it is easier to
separate the lithium-metasilicate(Li20.Si02) phase rather than the disilicate
phase (Li20.2SiO2).
In the high alumina-containingglasses i.e., when A1203/Li20 molar ratio
exceeds unity (glasses G4 and G5) , crystallizationbegan at lower temperature,
up to 1000' C, by the formation of the B-eucryptite s.s., in a characteristic of
prismatic or fibrous growths. This phase is characterized by low birefringence
and uniaxial negative optic figure. A concurrent deposition of a little amount
of clinoenstatite (MgSi03) was detected in some cases.

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

The most strikingphenomenonis the extensivemetastability

of the B-eucrypof the high A1203-containing
glassesat relatively
tite s.s. Crystallization
low temperaturebegan with the rapid formationof solid solutionsof a B-eucryphigherthan 1000 C led to partialor
tite type. Treatmentat temperatures
whole disappearance
of the B-eucryptiteS.S.
Oddly,the B-eucryptiteS.S. was stableover a wide range of temperature
solid solutionindicatesthat
ilOOOOC). The formationof this B-eucryptite-like
+.
a solid solutionof A13* and Li in B-quartzwas formedduringcrystallization
4+
substitutedby A13+ in pair with Li+
with, presumably,Si ions statistically
2+
ions.
and probablywith the other suitableMg
The B-spodumeneS.S. was apparentlyformedby crystallization
of the primarily
from
formedB-eucryptiteS.S. in most cases ratherthan by directcrystallization
glass &J.
The anomalyof the formationof the B-eucryptiteseriesat lower temperature
insteadof the expectedB-spodumenephase from glassesapproachingthe stoichioL16].
metric compositionof spodumenewas explainedby Kalininaand Fillipovich
The explanationwas that the phase most likelyto be formedfirst is one with
the lowestthe~odyn~ic potentialbarrierto the formationof a criticalnucleus capableof growth. It shouldbe assumedthat short range order of the
eucryptitetype arises in certainregionsof the glass,and that formationof
nuclei of the eucryptite-like
crystallinephase (metastable
under given conditions) occursmost easily from the kineticaspectswith the lowestbarriersto be
overcome. It shouldbe added that the symmetryof the hexagonalB-eucryptite
latticeis closerto the sphericallysymmetricalglass than that of the tetraof B-eucryptite
over
gonal B-spodumene.This also favoursthe crystallization
B-spodumene.

159

The B-eucryptite and B-spodumene are isostructural with silica polymorphs,

B-quartz and keatite, respectively, and form solid solutions with SiO2 and
MgA1204 [17,18].

In these stuffed silica derivative structures, A104 tetrahedra,

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.

2MgA1204 + 5Si02 --+

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,

0.67 Li20 - 0.33 MgO - 1.0 A1203 - 3.96 Si02

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

S. Ray and G.M. Muchaw, J. Am. Ceram. Sot. 51 (1968) 678.

Chi-Tang Li, Z. Kristallogr. 132 (1970) 118.

10 P.W. McMillan, Glass Ceramics, Academic Press, London, N.Y. (1979).

11 J.S. Machin, T.B. Yee and B. Hanna, J. Am. Ceram.

SOC.

35 (1952) 322

12 M. Tashiro, Proc. 8th Int. Cong. Glass (1968) 113.

--13 Tom F.W. Barth, Theoretical Petrology, IIed., John Wiley and Sons Inc., N.Y.,
London (1962).
14 1.1. Kitaigorodskii and R.Ya. Khodakovakaya, The Structure of glass, Vol. 3,
Consultants Bureau, N.Y. (1964) 27.
15 R.A. Eppler, J. Am. Ceram. Sot. 46 (1963) 99.
16 A.M. Kalinina and V.N. Filipovich, The structure of glass, Vol. 5,
Bureau
N.Y. (1965) 105.
17 D.A. Duke, and G.A. Chase, Applied Optics, 7 (5) (1969) 813.
18 S. Ray, J. Am. Ceram. Sot. 54 (4) (1971) 213.

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