Journal of Non-Crystalline Solids 17 (1975) 147-157

North-Holland Publishing Company

CALCULATION OF BULK MODULUS, SHEAR MODULUS AND

POISSON'S RATIO OF GLASS
Akio MAKISH1MA and John D. MACKENZIE
Materials Department, School of Engineering and Applied Science, University of
California, Los Angeles, Cal., USA
Received 20 August 1974
Combining Griineisen's equation with our Young's modulus equation of glass, new
formulae were semi-empirically derived for the calculation of bulk modulus, shear modulus and Poisson's ratio of glass. Considering packing density of atoms and bond energy
in unit volume the elastic moduli of glass can be calculated. The agreements between
calculated and observed values of the moduli of glass axe satisfactory for more than 30
glasses.

I. I n t r o d u c t i o n

Bulk modulus, shear modulus and Poisson's ratio o f glass have been studied by
many workers either to derive the relationship between chemical composition and
these elastic moduli or to interpret the structure of glass.
Spinner [1] and Weir and Shartsis [2] measured shear moduli or bulk moduli of
many optical glasses or alkali borate glasses by a dynamic method. Smyth [3] theoretically studied the possible mechanisms involved in the elastic deformation o f a
silicate glass and concluded that Poisson's ratio should be 0.25 if the work done
when glass is deformed consists in stretching or compressing the S i - O - S i links.
Soga and Anderson [4] showed that the bulk modulus o f glass or crystal is related
to the mean atomic volume and suggested that In K is inversely proportional to
tn(2M/Po), where K is the bulk modulus, M is the molecular weight, P is the number o f ions and p is the density.
The authors [5] theoretically derived an equation for the calculation o f Young's
modulus o f glass considering the packing density o f atoms and the bond energy per
unit volume. We further attempted to calculate the bulk modulus, shear modulus
and Poisson's ratio of glass from its chemical composition using the same approach
as in the previous work and found that combining Griineisen's equation, which defines the bulk modulus of solid materials, with our Young's modulus equation o f
glass, the elastic moduli can be calculated from the chemical composition. In this
paper, we report the derivation of the equations for the calculation of the bulk mo-

148

A. Makishima, J.D. Mackenzie~Calculation o f bulk modulus

dulus, shear modulus and Poisson's ratio of glass, and compare the calculated values
with the observed values of the moduli of over 30 glasses.

2. Theory
According to Grtineisen's first rule [6], the bulk modulus K is represented as
follows:
K V 0 = ~ mnlUoI ,

(1)

where V0 is the equilibrium volume found where the net force vanishes, m and n
are constants in Mie's equation, i.e.
(r) = - A i r m + B/r n ,

(2)

and U 0 is the equilibrium energy for volume V0 and is expressed for a ionic crystal
with the interatomic spacing r 0 as follows:
U 0 = [(m - n)/n] ( N a e 2 / r o ) ,

(3)

where N is Avogadro's number, c~ is Madelung's constant and e is the electronic

charge.
From eqs. (1) and (3) we obtain
K V 0 = m l m - nlN~e2 /9r 0 .

(4)

The equilibrium volume, V0, is related to the interatomic spacing, r 0, by the equation:
(5)

V 0 = CNr 3 ,

where C is a structural constant. From eqs. (4) and (5), the bulk modulus is calculated as follows:
K = (mlm-

nl/9C) ( e 2 / r o ) r ~ 3 .

(6)

The structural constant C is related to the packing density of ions as follows: for
an oxide A x O y , radii of which are r 1 and r 2, the equilibrium volume, V0, is related
to the interatomic spacing, ro, by
V 0 = CNr 3 = C N (r I + r2)3.

(7)

The packing density Vt is calculated by the equation:

Vt= 4 r r N ( X r ~ + y r 3 ) / 3 V o .

(8)

A. Makishima, ZD. Mackenzie~Calculation of bulk modulus

149

From eqs. (7) and (8) we get

1/C = 3/3 Vt/47r,

(9)

where
/3 = (r 1 + r2)3/(Xr~ + y r 3 ) .

(10)

The/3 values of various oxides can be calculated using Pauling's ionic radii.
We obtained an equation for the calculation of Young's modulus of glass, E, as
follows:
E = 2(e2/ro)ro 3 = 2V t G ,

(11)

where G is a dissociation energy per unit volume [5 ]. Combining eqs. (6), (9) and (11),
we get the following equation:
K = (mlm - nl/24rr)/3 V t E .

(12)

Eq. (12) shows that if we know m, n,/3, Vt and Young's modulus of oxide materials,
the bulk modulus can be calculated. However, for oxide glasses it is very difficult to
evaluate m and n which are important factors of Mie's atomic potential-energy equation. But eq. (12) indicates that the bulk modulus is correlated with the product of
packing density and Young's modulus. We examined this correlation for more than
30 glasses by calculating the packing density of the glasses. We obtained a good linearity between the observed bulk modulus and the product of the packing density
and the observed Young's modulus of the glasses (see fig. 1). Therefore, the slope
was determined to be 1.2 and the bulk modulus of glass can be expressed semi-empirically as follows:
K = 1.2 V t E = 2.4 v t 2 a .

(13)

Shear modulus S and Poisson's ratio/a are shown by the following well-known equations:
S-- 3EK/(9K - E) ,

(14)

p=E[2S-

(15)

1.

From these equations and eq. (13), we can get equations for the shear modulus and
for Poisson's ratio. Thus eqs. (14) and (15) can be rewritten as follows:
S = [3.6 Vt/(10.8 Vt - 1)1 E = 7.2 V2tG/(IO.S V t - 1),

(16)

ta = 0.5 - 1/7.2 Vt .

(17)

These equations indicate that bulk modulus, shear modulus and Poisson's ratio of
oxide glasses can be calculated if one knows the packing density and dissociation

150

A. Makishima, J.D. Mackenzie~Calculation of bulk modulus

1200

I000

800
"o
o

E
600
D
..Q
"17
>
i_

400

t/1
0

200

I
200

i
400

I
600

I
800

I
1000

I
Iz oo

Vt E ( Kb a r )
Fig. 1. Agreement between observed values of bulk modulus and products of packing density
and observed bulk moduli.
energy per unit volume o f oxide glasses. For the multicomponent oxide glasses,
Young's modulus was theoretically given in [5]:
E --- 83.6 Vt ~

GiX i .

(18)

This expression gives E in units of kbar if the unit o f G i, which is the dissociation
energy o f the ith oxide, is kcal/cm 3 and X i is the mole fraction of component i of an
oxide glass. Therefore, eqs. (13) and (16) can be rewritten as follows:
K = 100 V2t ~

GiXi,

S = [300 V2/(10.2 Vt - 1)] ~

(19)

aiX i .

(20)

3. Results and discussion

3.1. Silicate and other non-boron containing glasses

The bulk modulus, the shear modulus and Poisson's ratio o f silicate and other

A. Makishima, J.D. Mackenzie~Calculation o f bulk modulus

151

I000
L
rO
J31

"

800

2~
"0

o
E

600

-5

-I

4O0

-0
>

.~

200

200

400

600

800

Calculated

bulk

1000

modolus(Kbar)

Fig. 2. Agreement between observed values of bulk modulus and those calculated using eq. (19).

non-boron containing glasses were calculated using eqs. (17), (19) and (20) and
the results are compared with observed values (see figs. 2, 3 and 4). Figs. 2, 3 and 4
show a fairly good agreement between observed and calculated values. The straight
lines in these figures have a gradient of unity. The glass compositions used in these
calculations are given in table 1. These glasses are different from those used in
fig. 1. The observed bulk moduli, Poisson's ratios and densities of the glasses are
shown in table 2. Packing density Vt and dissociation energy per unit volume G i
were calculated by the method reported by the authors in [5].
3.2. Borate glasses

It is necessary to take into consideration the change of the coordination number

of boron in borate glasses. Using the method described in our previous paper [5], we
calculated the bulk modulus and shear modulus of some borate glasses. If we know
the fraction ~/of BO4 tetrahedra, two dissociation energies per unit volume, one for
BO 3 and one for BO4, can be used for the calculation of elastic moduli. For the
calculation of G i in eqs. (19) and (20), the G i should be
G B = 3, (G 4 - G3) + G3,
where G 4 = dissociation energy per unit volume for BO4 = 18.6 kcal/cm 3 and

(21)

152

A. Makishima, J.D. Mackenzie~Calculation o f bulk modulus

600

"E

500

q~
n

400

"O
o

300

-O

200

o~

b~
O

100

100

200

300

400

500

600

Calculated

shear

modulus( K bar)

Fig. 3. Agreement between observed values of shear modulus and those calculated using eq. (20).

_o

0.3

+-

-.

0.2

0.1

0.l

0.2
Calculated

0.3

Poisson's ra~rio

Fig. 4. Agreement between observed values of Poisson's ratio and those calculated using eq. (17).

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
~30

Glass
no.

76.8
72
69.6
71.1
69.2
68.2
66.8
64.6
61.7
68.9
66.8
7Z7
40.7
100
48.0
37.2
75
70
65
11.6
47.3
52.8
50
55
62.5
47.5
52.5
57.5
49.0
54.9

Si02

30.0
25.0
17.5
27.5
22.5
17.5

6.5

2.0

0.6
3.2
7.3
4.5
1.1

Na20

8.7
8.4
5.6
5.6
6.9
6.6
5.3
3.8
2.9
7.2
7.3
9.7

K20

Component oxides (mole%)

(mol%)

25
30
35

Li20

6.2
6.5

28.3
11.2
5.7

5.7
6.6

7.2

A1203

Table 1.
Compositions of glasses used in the present calculation.

11.8

52.4

10.3

CaO
0.3

13.6
16.4
17.5
18.8
22.8
25.2
27.9
31.6
35.4
6.9
9.5
3.1

7.7

7.1
7.7

BaO

PbO

7.9
8.7
3.0

ZnO

21.8
13.3

14.1
21.2
20.0
20.0
20.0
25.0
25.0
25.0
23.0
8.2

(MgO), 4.62 (ZrO2)

(MgO)
(TiO2)
(TiO2)
(TiO2)
(TiO2)
(TiO2)
(TiO2)
(MgO)
(MgO), 5.4 (ZrO2)

7.7 (MgO), 1.4 (ZrO2)

24.4 (MgO)
27.0
31.8

22.8
20.3 t

26.7 (MgO)
25.4

BeO

Other oxides
(mol%)

s,

E"

av

154

A. Makishima, D. Mackenzie/Calculation o f bulk modulus

Table 2
Observed bulk moduli, shear moduli, Poisson's ratios, densities and calculated packing densities
of various glasses.
Glass
no.

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30

Bulk
modulus
(kbar)
340
352
344
323
306
298
326
332
334
386
374
415
989
361
824
1005
494
509
498
798
813
742
500
501
494
526
530
523
876
744

Shear
modulus
(kbar)

Poisson's
ratio

density

Packing
density

Ref.

226
224
231
232
222
223
223
221
220
261
256
256
547
314
483
545
317
317
331
420
504
479
302
314
334
315
335
345
500
437

0.228
0.238
0.227
0.211
0.215
0.200
0.213
0.228
0.230
0.224
0.221
0.241
0.267
0.162
0.256
0.270
0.236
0.242
0.228
0.276
0.243
0.234
0.249
0.241
0.224
0.250
0.239
0.230
0.260
0.255

3.227
3.446
3.547
3.605
3.860
4.012
4.215
4.485
4.767
3.288
3.474
2.702
2.787
2.20
2.723
2.785
2.302
2.334
2.354
2.051
2.781
2.629
2.749
2.740
2.703
2.811
2.800
2.771
2.681
2.795

0.529
0.531
0.530
0.531
0.529
0.530
0.533
0.532
0.535
0.540
0.538
0.540
0.630
0.514
0.615
0.640
0.548
0.556
0.562
0.635
0.581
0.598
0.556
0.566
0.571
0.576
0.579
0.581
0.616
0.645

[ 1]
[ 1]
[ 1]
[1]
[1]
[1]
[1]
[1]
[1]
[1]
[1]
[1]
[7]
[1]
[7]
[7]
[8]
[8]
[8]
[8]
[8]
[8]
[9]
[9]
[9]
[9]
[9]
[9]
[7]
[7]

G 3 = dissociation energy per unit volume for BO 3 = 3.9 kcal/cm 3, 7 is the fraction
o f BO 4 tetrahedra in the glass. This equation was used for the calculation of Young's
m o d u l u s o f borate glasses.
The measured and calculated bulk m o d u l i and shear m o d u l i o f some borate glasses
are tabulated in table 3 and plotted in fig. 5. They show comparatively good agreem e n t considering the u n c e r t a i n t y o f experimental data and the a p p r o x i m a t i o n
underlying eqs. (19) and (20). The straight line in fig. 5 has a gradient o f unity.

3.3. Discussion
It is interesting to note that the shear m o d u l u s is partly expressed b y the square

A. Makishima, J.D. Mackenzie~Calculation o f bulk modulus

155

Table 3
Comparison of the measured and calculated bulk moduli and shear moduli of some borate glasses.

(mol%)

Bulk modulus (kbar)

Measured [8]
Calculated

Shear modulus (kbar)

Measured [8]
Calculated

100B20
5.6Na20-94.4B203
11Na20-89B203
17Na20-83B203
17Li20-83B203
17K20-83B203
17Cs20-83B203
22Na20-78B2Oa

121
190
250
290
330
240
200
350

69
110
130
160
190
120
90
180

Borate glass

105
160
210
250
336
213
182
300

71
97
123
145
191
130
118
172

of the packing density, and Young's modulus is correlated linearly with the packing
density as shown in eqs. (18) and (19). The bulk modulus is defined as the threedimensional isotropic pressure divided by the relative volume change. Therefore,
the bulk modulus would be more sensitive to the packing density. The shear modulus is related to the packing density in a complicated way shown in eq. (20), but for
oxide glasses Poisson's ratio is determined by the packing density as shown in eq.
(17). If atoms are loosely packed in the oxide glass, Poisson's ratio is small whereas
tightly packed glass has a higher Poisson's ratio. This seems reasonable because
Poisson's ratio is defined by the ratio of transverse to axial strain, and the transverse strain would be smaller in loosely packed glass as there is more space for the
atoms to move in.
400

Butk m o d u l u s
oShear modulus +. . /

"2

300

2oo

IO0

o<

00

100
Calculated

200
elastic

300

400

modulus(Kbar)

Fig. 5. Agreement between observed and calculated bulk moduli and shear moduli of some borate glasses [8].

156

A. Makishima, J.D. Mackenzie/Calculation o f bulk modulus

From eqs. (12), (14) and (15) Poisson's ratio and the shear modulus can be
theoretically expressed as follows:
S = [ m l m - nl ~ V t / ( 3 m l m - nil3 V t - 8zr)] E ,

(22)

/a = 0.5 - 4~r/mlm - n l ~ V t .

(23)

These equations show that Poisson's ratio as well as the shear modulus are correlated via a complicated expression in m and n which are important factors in Mie's
atomic potential-energy equation.
Shannon et al. [10] reported the most recently compiled atomic radii, and using
their atomic radii, we can get nearly equal or bigger packing densities than those
calculated using Pauling's atomic radii for glass compositions in table 1. Therefore, a
slightly better agreement between observed and calculated elastic moduli is obtained. In this paper we used Pauling's radii which are well-known.

3.4. A p p l i c a t i o n s

The results of the present study can be used to predict the chemical composition
of glasses with the highest possible bulk modulus and shear modulus.
The highest Young's modulus of oxide glass calculated would be closer to
16 102 kbar, assuming that the packing density is about 65% and Y~G i X i = 27.5
kcal/cm 3. Eqs. (19) and (30) show that the highest bulk modulus and shear modulus would be 11.6 102 kbar and 619 kbar, respectively, using the same assumption in the prediction of the highest Young's modulus of oxide glass, whose main
oxide constituents are BeO, AI203 and ZrO 2.
According to Laberge et al. [ 11 ] the density fluctuation in oxide glass, which
correlates with the intrinsic optical loss in fiber-glass wave guides for long-range
communication, can be expressed as follows:
Ap21p 2 = kTfl VKT ,

(24)

where k is Boltzmann's constant, Tf is the fictive temperature, K T is the bulk modulus and V is the scattering volume. Eq. (24) shows that a glass composition with a
lower fictive temperature and a high bulk modulus has a low density fluctuation.
Laberge et al. [11] reported that 50% Li20-B203 glass may be a suitable choice
for making optical fiber. This seems reasonable because, among alkali-borate glasses
which have comparatively low liquidus temperature, lithia borate glass has a higher
bulk modulus as the dissociation energy per unit volume of Li20 is fairly large
(19.2 kcal/cm 3) compared with that of Na20 (8.9 kcal/cm 3) or K20 (5.6 kcal/cm3),
and hence lowers the scattering as indicated by eq. (24).

A. Makishima, J.D. Mackenzie/Calculation of bulk modulus

157

Acknowledgements
This work has been supported by the Directorate of Chemical Science, AFOSR,
under Grant No. 70-1856 for which we are most grateful.
The authors are greatly indebted to N. Soga for constructive criticism of this
paper.

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]

[8]
[9]
[10]
[11]

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C.E. Weir and L. Shartsis, J. Amer. Ceram. Soc. 38 (1955) 299.
H.T. Smyth, J. Amer. Ceram. Soc. 43 (1959) 276.
N. Soga and O.L. Anderson, Proc. 7th Intern. Congr. on Glass, Brussels, Belgium, 1965,
vol. 1 (Institut National du Verre, Charleroi, Belgium, 1966) p. 9.
A. Makishima and J.D. Mackenzie, J. Non-Crystalline Solids 12 (1973) 35.
C. Zwikker, Physical Properties of Solid Materials (Interscience, New York, 1954) p. 90.
M.H. Manghnani, Elastic Parameters and Infrared Characters of Glasses under High Pressures and Temperatures, Final Report, Contract N00014-67-A-0387-0005, NR 032-515
(1970).
R.R. Shaw and D.R. Uhlmann, J. Non-Crystalline Solids 5 (1971) 237.
M.H. Manghnani, J. Amer. Ceram. Soc. 55 (1972) 360.
R.D. Shannon and C.T. Prewitt, Acta Cryst. B25 (1969) 925.
N.L. Laberge, P.K. Gupta, V. Vasilescu and P.B. Macedo, J. Non-Crystalline Solids 13
(1974) 164.