Journal of Non-Crystalline Solids 22 (1976) 305-313

North-Holland Publishing Company

CALCULATION OF THERMAL EXPANSION COEFFICIENT OF GLASSES

Akio MAKISHIMA and J.D. MACKENZIE
Materials Division, School of Engineering and Applied Science,
University of California at Los Angeles, California 90024, USA
Received 31 July 1975
Revised manuscript received 1 April 1976
Thermal expansion of oxide glasses has been theoretically studied to derive an equation for the calculation of the thermal expansion coefficient of glass from chemical composition. Gr[ineisen's constant may be correlated with packing density and a ratio of
cation-to-anion radius and, considering the packing density and dissociation energy per
unit volume, a semi emprical equation was derived. The agreement between observed and
calculated values was satisfactory over 150 glasses of the binary, ternary and quarternary
systems.

1. Introduction
The study of thermal expansion of oxide glasses is both scientifically and technologically interesting, for example, in the field of thermal strengthening of glass, thermal expansion coefficients of glasses are important for composite materials of glass
and metal or glass and polymer. Matching of thermal expansion coefficients and
Poisson's ratio are critical to make mechanically and thermally stable composite
materials.
The recent progress of the study of the thermal expansion of glass is well summarized in refs. [1 ] and [2]. According to these books more than 18 authors reported
empirical additive factors for the calculation of thermal expansion coefficients from
chemical compositions. Unfortunately, the additive factors vary for each of the
authors. Kumar [3] succeeded in the calculation of the thermal expansion coefficient
of non-metallic crystals by a semiempirical approach. However, because of their
complex structure, he reported empirical additive factors for glasses.
We are interested in a theoretical calculation of physical properties of glasses from
their chemical composition to develop new glasses possessing unique properties. This
is a very difficult problem because of the complicated structure of glasses. However,
as a first approximation we derived a semiempirical equation for the calculation of
thermal expansion coefficients of oxide glasses from their chemical compositions
and we have made a computer program for this calculation.
305

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A. Mak&hima, .I.D. Mackenzie / Thermal expansion coefficient of glasses

2. Theory
According to the Debye equation of state [4], the linear thermal expansion coefficient of solids can be thermodynamically shown as eq. (1).
(1)

= 7Cv/3K V ,

where 7 is Grfineisen's constant, Cv the heat capacity at constant volume, K the bulk
modulus and V the molar volume. Eq. (1) was derived thermodynamically for solids,
and we assume that the equation can be also applied to inorganic glass which is isotropic. If we can calculate these factors, the thermal expansion coefficient of glass
can be determined. Therefore, in the following, we studied how to calculate the values of these factors from chemical composition.
2.1. Bulk modulus K

Based on Griineisen's first rule the authors [5] derived equations for the calculation of bulk modulus and Poisson's ratio, ~t, of glass as follows:

lOO v 2,

GiX,,

/a = 0.5 - (1/7.2Vt),

(2)
(3)

where K is the bulk modulus in kbar, Vt the packing density, G i the dissociation energy per unit volume (kcal/cm 3) and X i the mole fraction of the ith component of
multicomponent oxide glasses. The packing density Vt [6], is defined by
- P ~ViXi,

(4)

where M is the molecular weight, p the density, X i the mole fraction of component
i, and V i the packing factor obtained from the following equation for an oxide
AxOy:
V i = 6.023 X 10234_3rr(XR c3 + YR3a) ,

(5)

where R c and R a are the respective ionic radii of metal and oxygen. Using these
equations we can calculate the bulk modulus and Poisson's ratio of glasses with fairly good agreement between observed and calculated values [6].
2.2. Heat capacity C v

For oxide glasses, heat capacity at constant volume C O is nearly equal to the heat
capacity at constant pressure Cp :

cv cp.

(6)

A. Makishima, J.D. Mackenzie / Thermal expansion coefficient of glasses

A o/

25

20

307

15

"0

IO
c_)
u

L
"6.
E

UJ

Y
i

I0

15

20

25

30

Cp(Cal/decj.rnole) of C r y s t a l s

Fig. 1. Relation between Winkehnan's empirical additive factors of heat capacity of glasses [7]
and the observed heat capacity of crystalline solids [8 ].

It is well known that heat capacity at constant pressure of glass can be calculated
by using Winkelman's empirical additive factors [7], Cpi, with good accuracy according to the following additive equation:

cp = ~ i C p i X i

(7)

Winkelman's empirical additive factors for constituent oxides of glass are plotted
against the heat capacity of oxides in the crystalline state, given in ref. [8]. The results are shown in fig. 1, and there is a good linearity. The solid line in this figure is
a slope of unity. Winkelman's additive factors were reported for a limited number of
common constituent oxides. Therefore, if the additive factor is not available for a
constituent oxide we may use the heat capacity of crystalline oxide in ref. [8].

2.3. Molar volume V

The molar volume V of oxide glass can be calculated by the following equation:

V = (~MiXi)/p.

(8)

A. Makishima, J.D. Mackenzie I Thermal expansion coefficient of glasses

308

2.4. Grfineisen's constant 7

Griineisen's constant 7 is generally expressed as follows [9,10]:
7-

1
6

1 0InK
2OlnV

31nF0x )

31nV

'

F(lx)= [( ll--~ )312 + 2512(ll +_~)3/21-1/3 .

(9)

(10)

Eq. (9) can be rewritten as follows:

v = 1

_ V{(I/2K)OK/a

V) + [ 1 1 F ( u ) l OF(u)IOV}.

(11)

This equation indicates that 7 is a function of V, K and DI.

For ionic crystal the molar volume V is generally expressed by the following equation [11 ]:

V = CNR 3 ,

(12)

where C is the structure constant whose values depend on the type of crystal structure, R the atomic spacing and N Avogadro's number. As the atomic spacing is a sum
of cation and anion radius, eq. (12) can be rewritten as follows:

V = CN(R c + Ra)3 = CNR3a [1 + (Rc/Ra)] 3 ,

(13)

where R e and R a are the radii of the cation and anion, respectively. For oxide glasses
the anion is oxygen, and the radius would be constant. Therefore, the molar volume
V can be a function of the ratio of cation-to-anion radius.
The bulk modulus and Poisson's ratio of glass are functions of packing density as
shown in eqs. (2) and (3). Thus 7 can be a function ofRc/R a and Vt. Eq. (11) shows
that 7 is a function of a product of V, which is related to Re/R a, and

{(1/~) OS'C/aV) + [1 IF(u)] aF(u)/3 V}.

The latter term is difficult to evaluate at this stage, but is partly related to the packing density of atoms because the volume change will be greater if this density is
smaller, which will reflect on the changes of bulk modulus and Poisson's ratio. Therefore, we assume that 7 can be expressed by a product ofRc/R a and Vt as a first approximation. We plotted the product against the observed Griineisen's constants of
various oxides [12], ionic crystals [13] and covalent glass [14] and found that the
product ofRc/R a and (V t -- 0.4) gives good agreement with the observed Griineisen's
constant as shown in fig. 2. The solid line in this figure is expressed by the following
equation:
3' = 11.2(V t - 0.4)(RclRa).

(14)

A. Makishima,J.D. Mackenzie / Thermalexpansion coefficient of glasses

309

2.4

20

'gg'

CaF2
~

1.6

~ l ~ 0e

'2
"~

0.8

//nZnO
~As2~3(9,ass

/ , GeO2(cjlass)

0.4

,~]203(gTa,~,.s
)
0

12

t6

ao

24

28

(Rc/RdXVt - 0.4)x 102

Fig. 2. Relation between observed GriJneisen's constant and a product of the ratio of cation-toanion radius and packing density.
This equation can be used for the calculation of Grtineisen's constant from chemical
composition.
However, eq. (14) cannot be directly applied for a glass of a multicomponent system, because the value o f R c varies according to the kinds of constituent oxide.
Therefore, the authors consider that ff the number of the m e t a l - o x y g e n bond A - O
is larger in the multiconrponent glass, the contribution of the A - O oscillator to
Grtineisen's constant would be greater according to its definition. Thus Grfineisen's
constant for a glass of a multicomponent system can be expressed by the following
equation:
7 = 11.2(V t - 0.4) ~ ( n c i / R a ) X i ,

(15)

where Rci is radius of the cation of the ith oxide and Xi the bond number fraction
of the ith oxide. For example, k i can be calculated for a 0.7SiO 2 0.3Na20 glass (in
mole fraction) as follows. According to Sun [15] the coordination numbers of Si and
Na are 4 and 6, respectively. The total number of metal-oxygen bonds in the glass
B t, is given by

B t=O.7N 1 4 + 0 . 3 N X 2 6 = 6 . 4 N .

(16)

310

A. Makishima, .I.D. Mackenzie / Thermal expansion coefficient of glasses

Therefore,
Xsio2 = 0.7N X 1 X 4/6.4N = 0.438,

(17)

XNa20

(18)

0.3N X 2 X 6/6.4N = 0.562.

2.5. Thermal expansion coefficient equation

As a conclusion to the foregoing sections, the variables of eq. (1) can be calculated,
and finally a semi-empirical equation for the calculation of thermal expansion coefficient of oxide glasses, c~, was derived as follows:

p [ l l . 2 ( V t - 0.4) ~(Rc/Ra)Xil[4.18
a =

(3Vt2 ~

GiXi ~ M i X i ) 1 0 4

~CpiXi]
(1/C),

(19)

where O is the density (g/cm3), Vt the packing density, Rc/R a the ratio of cation-toanion radius, Xi the bound number fraction of the ith oxide, Co the heat capacity
(cal/deg mole), Gi the dissociation energy per unit volume (kcal/cm3), M i the molecular weight of the ith oxide and X i the molar fraction of the ith oxide. Constant
4.18/100 is necessary to convert kbar and cal to cgs units.

3. Results and discussion

We made a computer program to calculate the thermal expansion coefficient of
oxide glasses from the chemical composition using the semi empirical equation. For
most silicate and borate glaases, if the chemical composition of a glass is known, its
thermal expansion coefficient can be calculated. To test eq. (19) we computed the
thermal expansion coefficients of over 150 glasses whose expansion coefficients and
chemical compositions are known. The calculation of the density of these glasses
was conducted by the method proposed by Huggins and Sun [16].

3.1. Binary system [ 17]

The thermal expansion coefficients of binary silicate, borate and phosphate glasses
were computed and the results are shown in fig. 3. The solid line is a slope of unity.
For the calculation of the expansion coefficients of borate glasses we took into account the boron anomaly for the calculation of bulk moduli. Considering the assumption underlying the thermal expansion coefficient equation, the agreement between
observed and calculated values is quite satisfactory.

A. Makishima, J.D. Mackenzie / Thermal expansion coefficient of glasses

311

200

150
>

#,

~/~8

I00
0

//~

zx

e 8oVzos-ZOP2Os
Na20- Si 02
K2O_ Si02

"5

Li20-Si 02

50

o Na20-B203
~20Pb0-808203

50

IO0

150

200

C~X loT(calculated)(I/C)

Fig. 3. Agreement between measured values of the thermal expansion coefficient and that calculated from eq. (19) for binary system glasses.

3.2. Ternary and quarternary systems [18]

The results of the calculation of the thermal expansion coefficients of ternary
and quarternary system glasses are shown in fig. 4. The solid line is a slope of unity.
The agreement is again fairly good. The deviations for most of the glasses were within

+15%.
In these calculations Pauling's atomic radii [19] of oxides and the dissociation
energy per unit volume of most oxide~ tabulated by the authors [6] were adopted.
3. 3. Discussion
Silica glass has a very low thermal expansion coefficient [20], and Baak [21 ] has
developed very low thermal expansion glasses containing copper oxide. Silica-titania
glass [22] is also a very low thermal expansion glass. The present equation is not applicable to the calculation of the very low thermal expansion coefficient of such unusual glasses.

312

A. Makishima, .I.D. Mackenzie / Thermal expansion coefficient o f glasses

200

150
.~,
"0
>
I,..

.~ I 0 0

o
p,.
0

:::::::::0::::i ,

'6

50

o~

~%-ca-si2
Z~ Na20_Be0_Si02

50

I00

150

200

C~ x 107( C a l c u l a t e d ) ( I / C )

Fig. 4. Agreement between measured values of the thermal expansion coefficient and that calculated from eq. (19) for ternary and quarternary system glasses.

4. Summary and conclusion

We derived a semiempirical equation for the calculation of thermal expansion coefficients of various oxide glasses from their chemical compositions. Although we
cannot apply the equation to abnormally tow thermal expansion coefficient glasses,
the equation is quite useful for the calculation of the expansion coefficient of comm o m glasses and the agreement between observed and calculated values is satisfactory over 150 glasses of the binary, ternary and quarternary systems.

Acknowledgement
This work has been supported by the Directorate of Chemical Sciences, AFOSR,
under Grant No. 7 5 - 2 7 6 4 for which we are most grateful.

References
[1 ] o.v. Mazurin, A.S. Totesh, M.V. Strel'tsina and T.P. Shvajko-Shvajkovskaya, Heat expansion of glass (Academy of Science, Leningrad, 1969).

A. Makishinta, J.D. Mackenzie / Thermal expansion coeffident of glasses

313

[2] M.G. Graham and H.E. Hagy, eds., Thermal expansion - 1971, AlP conf. Proc. No. 3
(American Institute of Physics, New York, 1972).
[3] S. Kumar, Cent. Glass Ceram. Res. Inst. Bull. 7 (1960) 58.
[4] B. Yates, Thermal expansion (Plenum Press, New York-London, 1972) pp. 33-36.
[5] A. Makishima and J.D. Mackenzie, J. Non-Crystalline Solids, 17 (1975) 147.
[6] A. Makishima and J.D. Mackenzie, J. Non-Crystalline Solids 12 (1973) 35.
[7] A. Winkelman, Ann. der Phys. und Chem. 49 (1893) 401.
[8] R.C. Weast, ed., Handbook of chemistry and physics, 52nd edn. (The Chemical Rubber Co.,
1971-1972).
[9] J.C. Slater, Chemical physics (McGraw-Hill, New York, 1939) pp. 2 9 , 2 1 6 - 2 2 0 , 2 3 4 - 2 3 8 .
[10] F.W. Sheard, Phil. Mag. 3 (1958) 1381.
[11 ] P. Seitz, The modern theory of solids (McGraw-HiU, 1940) p. 79.
[121 N. Soga, J. Appl. Phys. 40 (1969) 3382.
[13] E. Gruneisen, Handbuch der physik, vol. 10 (Springer, Verlag Berlin), 1926) p. 22.
[14] R. Ota, N. Soga and M. Kunugi, Yogyo-Kyokai-Shi (J. Ceram. Soc. Japan) 81 (1973) 156.
[151 K.-H. Sun, J. Am. Ceram. Soc. 30 (1947) 277.
[16] M.L. Huggins and K.-H. Sun, J. Am. Ceram. Soc. 26 (1943) 4.
[17] M.D. Karkhanavala, Glass Ind. 33 (1952) 403.
[18] M.D. Karkhanavala, Glass Ind. 33 (1952) 458,526.
[19 ] L. Pauling, Nature of the chemical bond 2nd ed. (Cornell University Press, Ithaca, New
York, 1940).
[20] O.L. Anderson and G.J. Dienes, Non-crystalline solids, ed. V.D. Frechette (Wiley, New
York-London, 1960) p. 449.
[21 ] N.T.E. Baak, US Pat. 3,528,829 (1970).
[22] G.J. Copley, A.D. Redmond and B. Yates, Phys. Chem. Glasses, 14 (1973) 73.