JOURNAL OF MATERIALS SCIENCE LETTERS 7 (1988) 33-35
Effect of MgO additions on the glass transition temperature of
Li20-AI2Oa-SiO2 glasses
D. N. C O O N , R. M. N E I L S O N JR
Idaho National Engineering Laboratory, EG&G Idaho, Inc., Idaho, USA
The effect of atomic-level structure on the physical
properties of glasses has been the subject of numerous
investigations which have been reviewed in detail else-
where [1-3]. The objective of this communication is to
propose that the glass transition temperature is related
to atomic structure and, hence, chemical composition
in a systematic manner. The transition temperature is
characterized by short-range atomic relaxations, and
signifies the beginning of the transformation range.
Properties of the glass change from those of a solid to
those of a supercooled liquid in the transformation
range. It is not surprising, therefore, that the trans-
ition temperature is observed at an invariant viscosity
( a p p r o x i m a t e l y 1013 to 1013'5 P) in nearly all silicate-
based glasses [3]. It can be hypothesized that changes
in the atomic structure which greatly affect viscosity
will also have a pronounced effect on the glass trans-
ition temperature.
Because the glass has a finite viscosity at the trans-
ition temperature, one portion of the structure must
be mobile relative to another position. Bonds must be
broken to accommodate such mobility. The modify-
ing io~oxygen bonds, being weaker than the network-
forming bonds, would be expected to break preferen-
tially. It follows intuitively that both the number of
modifying ion-oxygen bonds, which determines the
number of nonbridging oxygen (NBO), and the
strength of the individual modifying ion-oxygen bond
would be two factors which dominate viscosity and,
hence, the transition temperature. The number of
NBO would also determine the size of the structural
units that are mobile (flow units). A highly modified
structure with large numbers of NBO would degenerate
to smaller flow units than would a highly polymerized
structure containing low numbers of NBO.
Gutzow [4] derived the following relationship for
polystyrene
(Tg) -1 = a + b(p)-I
P defines the degree of polymerization and indicates
that as the structure becomes more "cross-linked", the
transition temperature (Tg) increases. Eisenberg and
Takahasi [5] defined P for alkali-silicate systems in the
following way
[M20 ] P + 1
[SiO2]
-
P
where the concentration of alkali oxide is given by
[M20] and the concentration of silica is given by
[SiO2].
Typically, oxide glass structures are characterized
by the average number of NBO per tetrahedron,
NBO. NBO can be calculated [6] according to:
NBO = 2
I [O2 ]7
[Si4+]j - 4 (3)
Combining Equations 1, 2 and 3
(Tg) t = a + b(NBO) (4)
Equation 4 predicts the expected trend that as more
NBO are present in the structure, the transition
temperature decreases.
Eisenberg and Takahasi [5] related the transition
temperature to the coulombic force between the modi-
fying ion and oxygen ion:
The coulombic force between the modifying ion and
oxygen is proportional to ( Z / R ) where Z is the charge
on the modifying ion and R is the ionic radius. This
relationship was shown to hold for silicate and
phosphate glasses, and it was concluded [5] that the
coulombic force was more important than the number
of NBO in determining Tg.
In the present study, the effects of MgO substitution
for Li20 was investigated in aluminosilicate glasses.
Both Li ÷ and Mg 2÷ exist in six-fold coordination
with oxygen and are approximately the same size,
0.06 and 0.065 nm, respectively. Glasses in the MgO-
Li20-A1203-SiO2 family were prepared by melting
reagent grade oxide and carbonate powders in alumina
crucibles at 1500 to 1600°C for 1 to 2 h. The glasses
were quenched in air, ground to a powder ( - 63 #m),
analysed for cation concentration, and examined by
differential thermal analysis to determine the glass
transition temperature.
The analysed chemical compositions of the glasses
studied are given in Table I. In addition to the con-
(1)
centrations shown in Table I, each glass contains
2.7 wt % TiO2 as a nucleating agent to promote crystal
growth during heat treatment. The average nonbridg-
ing oxygen concentration (NBO) was calculated by
assuming that AP ÷ and Ti4÷ ions acted as network-
forming cations like Si 4+ according to
[O2-] -4 (6)
(2) NBO = 2 [Si4+] + [Ap+ ] + [Ti4+]
The relationship of NBO with the inverse of trans-
ition temperature, as determined by differential ther-
mal analysis, is shown in Fig. 1. The data for glass
compositions with NBO ~< 0.5 follow the trends
predicted by Equation 4 very well; however, for glass
33
T A B L E I Analysed compositions (mol%) of glasses prepared 690 I I I
in this study

Composition SiO2 A12 0 3 Li20 MgO

. /
~" 640- " / -
/
3a-T 53.8 lY7 32.5 0.0
3b-T 54.6 13.6 26.0 5.8
3c-T 58.2 13.6 16.0 12.2
3d-T 58.4 13.7 9.1 18.8 i Correlation
3e-T 60.0 14.5 0.0 25.5 590 -- coefficient = 0 . 7 7
5a-T 56.3 7.6 22.6 13.5
.o
r-
6a-T 49.2 10.2 17.6 23.0
7a-T 58.3 8.0 16.3 17.4

~- 540-
compositions with NBO >/ 0.5, the expected trends
are not observed. The data suggest that the size of the
flow unit is the dominant factor in determining the
transition temperature only for large flow units, as
would be expected for highly polymerized networks
490 --
/.
I I I
(NBO < 0.5). Other parameters must dominate the 1.5 2.0 2.5 3.0 3.5
transition temperature for compositions with higher I~1109 J}
concentrations of modifying ions (NBO > 0.5).
The energy required to bring the two ions from an Figure 2 Effect of the calculated average strength (if/) on the
modifying ion-oxygen bonds on the glass transition temperature of
infinite separation (R = oe) to the equilibrium MgO-Li20 A1203 SiO2 glasses.
separation (R = R0) can be described using Coulomb's
law
be described by the linear relationship
f~o 1 Zl Z2
energy = 4ga~ R 2 dr (7) Tg = a + b(ffz) (10)

1 ZtZ2 There is a significant amount of scatter in the data as

indicated by the correlation coefficient of 0.74 for the
4zce0 R0
linear regression.
The strength of a bond (the work, W, required to As NBO correlates well with the data for
break the bond) is the negative of the energy calcu- NBO < 0.5, and if/gives a fair correlation over the
lated from Equation 7 entire range, it is reasonable to expect that both para-
meters affect the transition temperature to some
- 1 Zt Z2
w - (8) extent. With this in mind, the data were fit to the
4z~e0 R0 two-parameter linear relationship
Fig. 2 shows the variation of Tg with the average work Tg = a' + b'(NBO) + c'(l,P) (11)
(W) required to break a modifying ion-oxygen bond
calculated from Equations 4 and 10 would predict that b' < 0 and
= _ "M 2+1
c' > 0. Consistent with those predictions, the two-
if/ 1 WLi+[Li+] + WMg2+[ g 1 (9) parameter regression yields a' = 252.5 + 1.0,
6 [Li +] + [Mg 2+ ] b' = -115.8 _ 0.7, c' = 146.5 _ 0.4. The plus-or-
The term (1/6) in Equation 9 results from the six-fold minus value indicates the 95% confidence interval.
coordination of both Li + and Mg 2+ with oxygen. The correlation coefficient of the multivariate regres-
Consistent with Equation 5, Fig. 2 shows the data can sion is 0.96, indicating an excellent fit to the experi-
mental data.
It can be concluded that both the number of NBO
~" 2.5 and the strength of the individual modifying ion-
o
b I I I I I I ° I 91o I oxygen bond affect the glass transition temperature
for the MgO-Li20-AI203-SiO 2 glasses prepared. As
2.0 NBO increased, the transition temperature decreased,
and as if/ increased, the transition temperature
increased. When the structural parameters were con-
sidered separately, as was the case with previous
E 1.5 models, neither adequately correlated with the data
g over the entire range of compositions investigated.
- O~rrelatio n coefficient = 0.85/ The two-parameter, linear model presented in this
# study considered both parameters concurrently, and
1,C I/I I I I I I I / was found to provide an excellent fit with experiment-
0 0.2 0.4 0.6 0.8 1.0 al data for the glass system studied.
NBO
Figure 1 Effect of calculated average nonbridging oxygen concen- Acknowledgements
tration (NBO) on the glass transition temperature. The authors gratefully acknowledge S. T. Schuetz for

34
providing the differential thermal analysis, and K. 3. R. H. DOREMUS, "Glass Science" (Wiley, New York,
1973).
Messick and J. G. Jolley for the chemical analyses.
4. I. GUTZOW, Phys. Chem. 221 (1963) 153.
This work was supported by the US Department of 5. A. EISENBERG and K. T A K A H A S H I , J. Non-Crystalline
Energy, Office of Fossil Energy, under DOE Contract Solids 3 (1970) 279.
no. DE-AC07-76ID01570. 6. W. D. KINGERY, H . K . BOWEN and D. R. UHL-
MANN, "Introduction to Ceramics" (Wiley, New York,
1976) p. 105.
References
1. H. RAWSON, "Glass Science and Technology 3: Properties
and Applications of Glass" (Elsevier Scientific, Amsterdam,
1980).
2. P. BALTA and E. BALTA, "Introduction to the Physical Received 9 June
Chemistry of the Vitreous State" Abacuss, Kent, 1970). and accepted 16 June 1987

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