Journal of Non-Crystalline Solids, 15 (1974) 153-164.

North-Holland Publishing Company

VICKER'S HARDNESS OF GLASS

M. YAMANE * and J.D. MACKENZIE
Materials Department, School of Engineering and Applied Science, University of California,
Los Angeles, California, USA
Received 9 October 1973
An equation has been derived for the direct calculation of Vicker's hardness number of
glasses from their chemical compositions. The method is based on a consideration of deformation during indentation, which was related to Young's modulus and the average single bond
strength of a glass.
Excellent agreement is obtained between calculated and measured values of Vicker's hardness number for a variety of glasses.

1. Introduction
Many investigations of glass hardness have been conducted primarily to compare
and correlate hardness values with other physical properties or with structure and
bonding [ 1 - 9 ] . In most cases, however, only general trends could be established
between hardness and glass structure or other physical properties. The difficulty of
this problem is obviously due to the complex nature of the deformation which leads
to the formation of indentation for the hardness measurement as well as our limited
knowledge of glass structure. For instance, even among glasses of the same system,
the indentation patterns are different [10].
In this investigation, we have attempted to correlate the Vicker's hardness of
glasses with their bond strengths and elastic moduli in order to obtain greater understanding of the meaning of hardness. The objective is to permit the approximate
prediction of hardness from chemical compositions.

2. Considerations on the deformation during indentation

Vicker's Diamond Pyramid Hardness is determined in practice by measuring the
diagonal length of the indentation produced by the penetration of a square-based
pyramid having an angle of 136 between opposite pyramid faces. The hardness
* Present address: Tokyo Institute of Technology, 2-12-10okayarna Meguro-ku, Tokyo, Japan.

154

M. Yamane, J.D. Mackenzie, Picker's hardness of glass

number H v is given by the relation

Hv -

2L sin 0
d2

(1)

where L is the applied load, d is the average value of the diagonals and 0 is 136 .
Although the diagonal, d, in eq. (1) is obtained by measurement after the removal
of the load, it is known that the change in the lengths of the diagonals upon unloading is very small [6] and almost insignificant when compared to the diagonal length
itself. The experimentally measured diagonal, then, approximately represents the
diagonal of the indentation at the time when the penetration of the indentor ceases.
So, the hardness is directly related to the size of the indentation.
The main factors to be considered in the indentation process are nature of stresses
involved in the process, nature of deformations caused by those stresses, kinds of
resistances to those deformations, the relationship between these resistances and the
relation between the hardness number and these factors.
Although the precise stress distributions in the indentation process are unknown,
it may be assumed that the material undergoes both compression and shear, and
these two stresses are primarily responsible for the various deformations which in
turn give rise to the formation of the observed indentation.
Among the deformations which are supposed to be caused by one or the combination of these two stresses, those which have been experimentally observed in glass
are [10-12], flow due to shear, elastic deformation caused by comparison and two
types of densification resulting from compression and shear, one involves the breaking
of bonds and the other does not. This last type of deformation, namely densification,
is characteristic of glass because of its random structure.
The fact which makes the understanding of glass hardness difficult is that the ratio
of the contribution from various deformations to the formation of an indentation is
not the same but varies with glass composition. For example, as seen in table 1, the
relative volume caused by material transport in various deformations is quite different between SiO 2 glass and CaO SiO 2 glass, [10], despite the similarity of their
hardness numbers.
This dependence of the volume ratio on the glass composition and hence structure
has long been the reason for controversy about indentation mechanisms. For instance, results on soft glass may best be explained by considering the so-called 'pile-up'
due to plastic flow while those for hard glass like silica may be preferentially treated
by considering densification [ 13].
The numbers in table 1 suggest that not only one particular deformation, but all
three mechanisms can be operative in the indentation of glass, and the ratio of contributions from each deformation is determined by the mutual relation of the resistances characteristic of various deformations.
Since hardness number is obtained from the diagonals of indentation as a result
of the combination of all deformations, all the factors determining the various deformations are of importance to the hardness of a glass.

155

M. Yamane, J.D. Mackenzie, Vicker's hardness of glass

Table 1

Comparison of contributions from various deformations to the formation of indentation for

Si02 and CaO Si02 glass.
Glass

Hardness
(kg/mm2)

SiO2
635
0.5CaO 0.5SIO2 650

Elastic
deformation
(%)

Densification (%)
recoirrecoverable verable

Plastic
flow

37
22-27

50 -60
15-20

negligible
6%

10
50-55

The numbers were estimated from ref. [10] assuming that the volume % corresponding to each
deformation is represented by the volume % of recovery, in the order, elastic recovery, recovery
by annealing below Tg, amount after subtraction of pile-up volume from the rest, and pile-up
volume.
Let us first consider the resistance of a glass to various deformations. For the
elastic deformation, since it is caused by compression, the logical parameter to relate
to the resistance is perhaps the bulk modulus, although the compression is not applied hydrostatically. For the irreversible flow, caused by shearing stress, it is probable that breaking of chemical bonds is involved. The parameters to show the resistance to this type of flow may be the combination of shear modulus, G, defined
for a recoverable process and some factor related to the average bond strength, a.
In the case of densification, the situation is more complicated since this process is
caused by both compression and shear, and it may also involve the breaking of bonds,
depending on the bond strength of the constituent elements.
Although we have no experimental data on the effect of bond breaking on densification, qualitatively the breaking of bonds will make the movement of ions easier.
Thus, the resistance to densification will be larger in systems composed of elements
having strong bonds. Then the factor related to bond strength, a, is again one of the
important parameters, as well as the shear modulus, G, and the bulk modulus K.
In summary then, we assume that the resistance, Re, to elastic deformation and
that to flow, Rf, are expressed as:
R e cr K

and

Rfcc (c~G) ,

(2)

where K is bulk modulus, o~is bond strength factor, and G is shear modulus. For
the resistance to densification, Rd, which is caused by the simultaneous action of
two stresses,

R d ~x { (aG)K}.

(3)

In order to relate these resistances with the hardness number, Hv, it is necessary
to consider the mutual relation of these deformations during the indentation process.
One of the experimental facts which has an important bearing on this problem
is the results of quantitative measurement of the recovery of indentations by Neely
[10]. According to Neely, the ratio of the volumes recovered by various heat treatments is independent of applied load for the same glass. Now the size of the inden-

156

M. Yamane, J.D. Mackenzie, Vicker's hardness o f glass

tation varies with applied load. Thus, if each volume observed in a recovery process
represents the volume change caused by each independent deformation in the indentation process, the ratio of the volume change due to each deformation is constant
for any size indentation for the same glass. This suggests that the ratio of the volume
change for each deformation accompanied by any infinitesimal increment of indentation volume may also be constant.
It is therefore likely that all the deformations proceed in a parallel fashion in the
indentation process. In the process of penetration of an indentor, the area supporting the applied load increases. Accordingly, the stress acting on the unit area of indentation surface decreases with increasing penetration. The magnitude of this
changing stress per unit area is directly related to the magnitude of both shearing
and compressive stresses at any instant during indentation. Further, any material
transport caused by these stresses can increase the indentation surface and thus result in relaxation. In other words, without regard to the type of deformation, the
stress supported by the indentation surface is the same, if an equal amount of material transfer is caused by the same load.
Since all three deformations are supposed to proceed in parallel, the ratio of the
contribution from each deformation, or the route to reach the final state where no
further material transfer occurs, will be determined by the condition to minimize
the overall resistance with respect to the formation of indentation.
For example, in a glass-like fused silica the bulk modulus of which is relatively
small (3600 kg/mm2), elastic deformation occurs more easily than plastic flow
which must proceed against relatively high shear modulus (3200 kg/mm 2) [14] and
large single bond strength (106 kcal/mol of bonds) [15 ]. However, in a glass like
CaO SiO 2 glass, the bulk modulus is high (about 6000 kg/mm 2) but the shear
modulus (about 3000 kg/mm 2) and the average bond strength (about 57 kcal/mol
of bonds) are relatively small. Here, plastic flow is easier than elastic deformation.
The conditions for the ceasing of penetration will be determined by the relation
between the stress per unit area and the total resistance to material transport by a
combination of the three types of deformations.
As the hardness number, Hv, by definition, is the load divided by the area of
contact at the time when the penetration ceases, it reflects the stresses acting on
the unit area at that moment.
Then, the condition for the ceasing of the penetration will be given by
Itv/R = C

or

= CR ,

(4)

where H v is hardness number, R is the total resistance and C is a constant related to

the ratio of the stress to deformation resistance at the time penetration ceases. That
is, the indentation will cease when the stress per unit area has decreased to a value
to give a constant ratio, C, with respect to the combined resistance, R.
If we can express the combined resistance,R, in terms of R e, Rf, R d for respective deformations, the hardness of glass can also be expressed from intrinsic properties such as bulk modulus, shear modulus and so on.

M. Yamane, J.D. Mackenzie, Vieker's hardness o f glass

157

As we have considered in the above, all three types of deformatiop~s are supposed
to proceed in such a way as to minimize the combined resistance, R, for the formation of an indentation. Then, the most probable form of R will be again the geometrical average of three resistances which is:
R = (ReRfRd)1/3

(5a)

Now
R o: [(K)(o:G)(aGK)I/2]I/3

(5b)

and
[( K)(otG)(otG K)I/2 ] 1/3 = (aG K)I/2 .
.'. R c~ (o~GK)I/2 .

(5c)

Re, Rf and R a are resistances to compression, shear and densification.

Accordingly, from eqs. (4) and (5),
H v = C' (otGK) 1/2 ,

(6)

where C' is the proportional constant to give the ratio of the stress to the resistance
to deformation at the time when indentation ceases.
In order to determine the proportional constant C' in eq. (6), we need the actually measured value o f H v. If we now take Si-O bond and SiO 2 glass as the arbitrary
standard to determine the relative bond strength factor, a, (i.e., a = 1 for SiO 2 glass),
the constant C' is estimated by substituting Hv, K, and G of measured values for
SiO 2 glass, 650 kg/mm 2 [1,2, 9-11], 3600 kg/mm 2 and 3200 kg/mm 2 , to be 0.19.
The equation for the Vickers hardness number of glass is then
H v = 0.19 ( a G K ) 1/2 .

(6a)

3. Equation for the calculation of hardness number

Eq. (6) shows that it is possible to estimate the hardness number of glass if both
shear and bulk moduli and average single bond strength are known for the given
glass.
In an isotropic material such as glass, both bulk modulus and shear modulus are
known to be related to Young's modulus and Poisson's ratio by the equations:
K

E
3(1-2v)

(7a)

and
G-

E
2(l+v) '

(7b)

158

M. Yamane, J.D. Mackenzie, Vicker's hardness o f glass

where E is Young's modulus, K, the bulk modulus, G, the shear modulus and v,
Poisson's ratio.
Young's modulus for silicate glass can be obtained from glass composition by an
empirical relation using factors given by Phillips [16], Williams and Scott [17], or
from equations derived by Makishima and Mackenzie [25]. Poisson's ratio, v, is related to ionic volume fraction of glass [18] as
v= 1.12 V - 0.313

for

0 . 4 < V<0.475

(8a)

for

0.475 < V < 0.55

(8b)

and
v = 1.04 V - 0.277
or approximately
v = 1.1 V - 0.3,

(8c)

where v is Poisson's ratio and V the ionic volume fraction.

Substituting eqs. (7a), (7b) and (8a) into eq. (6a), the hardness number, H v, becomes
1/2
Hv = 0.051 (
a
)
0.462 + 0.09 V - V2
E.
(9)
The value of(x, the ratio of average single bond strength to Si-O bond strength, is
given by the relation,

a =

(10)

where f/is the number of cations, ], in one mole weight of glass, n], the coordination
number, ej, the single bond strength of cation ] to oxygen bond, and esi the single
bond strength of the Si-O bond.
The ionic volume fraction is calculated from glass composition and density, assuming a glass to consist of spherical ions of radius r i. Thus
P

V=ff

Z)

(11)

where V is ionic volume fraction, p, the density, M, the molecular weight of glass,
ri, the radius of the ion, i, and f i the number of the ion, i, in one mole weight of

glass.
Since the density of a glass can be estimated using factors given by Huggins and
Sun [19], and the coordination number and single bond strength are available from
Sun's table [15], all the parameters in eq. (9) are obtainable for silicate glass if the
composition is known.

M. Yamane,J.D. Mackenzie, Vicker'shardness of glass

159

4. Typical example of hardness calculation

The practical calculation from chemical composition of glass hardness using eq.(9)
is carried out by obtaining Young's modulus, E, relative bond strength factor, c~, and
ionic volume fraction, V, of glass. The calculation in the case of 20Na20 10CaO
70SiO 2 (mol %) glass, for instance, is as follows:

4.1. Calculation of Young's modulus, E, of the glass

According to Phillips [16], the Young's modulus, E, of the glass is given by the
relation:
E = XNa20 ENa20 + XCaO ECaO + XSiO2 ESiO2 ,

(12)

where ENa20 , Eca O and Esio~ are Young's modulus coefficients (in kbars/mol %),
and XNa20 , )(Ca O and Xsio2 are molar percentages of Na20, CaO and SiO 2 in the
glass.
Substituting the values of coefficients of Phillips [16]:
ENa20 = 2.6,

Eta O = 12.6,

ESiO2 = 7.3

(13)

XCaO = I0 ,

Esio2 = 70,

(14)

and
XNa20 = 20,

into eq. (12) we obtain

E = 689 (kba0 --- 7020 (kg]mm2).

4.2. Calculation of relative bond strength factor,

In the glass of the above composition, the numbers of respective cations fN a, fCa,
fsi in one mole weight of glass are:
fNa = 2XNa2ON = 0.4N,

fSi = Xsio2 N = 0.7N,

(15)
where XNa20, XCaO and Xsio2 are mote fractions of Na20, CaO and SiO 2 and N is
Avogadro's number. The coordination numbers of Na, Ca, Si are 6, 8 and 4 according
to ref. [6]. That is,
nNa = 6,

nca = 8 ,

fCa = XCa20N = 0.1 N,

nsi = 4.

(16)

And the single bond strengths (kcal) of these cation-to-oxygen bonds are
eNa = 20IN,

eca = 32/N,

esi= 106/N.

(17)

Then the relative bond strength factor, a, is directly obtained by substituting

eqs. (15), (16), (17) into eq. (10) which is

160

M. Yamane, J.D. Mackenzie, Vicker'shardness of glass

~fNa nNa CNa + fCa nca ~Ca + fsinsi eSi )

o~=

eSi {fNa nNa +fcanca+fsinsi )

(10a)

i.e., a = 0.583.
4. 3. Calculation of ionic volume fraction V
Among the factors in eq. (11) needed to calculate the ionic volume fraction, the
molecular weight of glass, M, is the simple summation of the products of mole fraction and the molecular weight of respective oxide constituents. This is
M = XNa20 MNa20 + XcaO MCaO + Xsio2 MSiO2
= 0.2 X 61.99 + 0.1 X 56.0 + 0.7 X 60.06

(18)

= 60.0 (g/mol).
The density, p, is obtained from the specific volume Vs estimated by weight
fractions, ICNa20, WCaO and ISIO2, and the volume factors VNa20, VCao and VSiO2
given in ref. [19] for Na20, CaO and SiO 2 by the relation
1/p = Vs = VNa20 WNa20 + VCaO WCaO + VSiO2 ICsi02 .

(19)

In the present example, weight fractions of Na20, CaO and SiO 2 are
WNa20 = 0.207,

WCaO = 0.093,

WSiO~ = 0.700

(20)

and the ratio, NSi, of the number of Si atomsfsi, to that of 0 atomsf0 in glass is
fsi _
Xsi02
_ 0.7 _ 0.41
Nsi - f o
XNa20+ Xcao + 2Xsio2
1.7

(21)

Therefore, the volume factors, according to ref. [19], for Na20, CaO and SiO 2 are:
VNa20 = 0.324,

VCaO = 0.231,

VSiO2 = 0.441.

(22)

Substituting eqs. (20) and (22) into eq. (19), the density of the glass is
1/p = Vs = 0.397 (cm3/g),
0 = 2.52 g/cm 3 .

(23)

According to Goldschmidt, the ionic radii of Na, Ca, Si and O are:

rNa = 0.98 A, rca = 1.06 A, rsi = 3.39 A,

r O = 1.32 A

(24)

and the numbers of respective ions in one mole weight of glass are:
fNa = 0.4N,

fCa = 0.1 N,

fsi = 0.7N,

fO = (XNa20 +Xcao + 2Xsio2 ) N = 1.7N,

where N is Avogadro's number.

(25)

M. Yamane, J.D. Mackenzie, Vicker's hardness of glass

161

Table 2
Comparison of calculated hardness with measured value.
Ref.

Hardness
measured
(kg/mm 2 )

SiO2

[ 10]

635

650

2.4

50CaO 50SIO2

[ 10]

620

680

9.7

55CAO 45SIO2

[ 10]

620

652

5.2

33.3Li20 66,7SIO2

[ 101

530

587

10.7

16.7Li20 16.7KzO 66.6SIO2

[ 10]

495

491

-0.8

11.1Li20 " 2 2 . 2 K 2 0 66.7SIO2

[ 10]

460

429

-6.7

3 3 . 3 K 2 0 66.7SIO2

[ 10]

335

333

-0.6

25NazO " 5CaO 70SIO2

[ 2]

487

457

6.1

20Na20 10CaO 70SiOz

[ 2]

554

511

-7.8

1 5 N a 2 G ' 15CAO 70SIO2

[2]

605

556

-8.4

10Na~O 20CaO 70SIO2

[ 21

620

610

- 1.6

19Na20 5CaO ' 76SIO2

[2]

501

492

-1.8

Glass (mol %)

Hardness
calculated
(kg/mm 2 )

Error
%

18Na20 " 10CaO ' 72SIO2

[ 2]

562

520

-7.4

17.5Na20 12.5CAO ' 70SIO2

[2]

583

535

-8.2

17Na20 ' 15CaO 68SiO~

[2]

603

542

- 10.1

16Na20 20CaO 64SIO2

[2]

594

561

-5.4

15Na20 " 25CAO 60SIO2

[21

588

590

0.3

12.5Na20 12.5CAO 75SIO2

[6]

629

575

-8.6

12.5K20 12.5CAO 75SIO2

[6]

611

522

-14.6

12.5Na20 12.5BaO 75SIO2

[6]

538

491

-8.7

12.5K20 12.5BaO 75SIO2

[6]

491

457

-6.9

1 2 . 5 N a 2 0 12.5PbO - 75SIO2

[6]

522

450

-13.8

12.5K20 12.5PbO 75SIO2

[6]

459

427

-7.0

11.8Na20 88.2SIO2

[2]

505

490

-3.0

19.SNazO 80.5SIO2

[2]

405

430

6.2

23.3Na20 76.7SIO2

[2]

375

409

9.1

27.0Na20 73.0SIO2

[2]

362

394

8.8

30.8Na20 69.2SIO2

[2]

354

386

9.0

12.1K20 87.9SIO2

[2]

406

413

1.7

15.8K20 84.2SIO2

[2]

374

390

4.3

17.7K20 82.3SIO2

[2]

359

379

5.6

19.6K20 80.4SiO2

[ 2]

364

370

1.6

2 3 . 0 K 2 0 ' 77.0SiO2

[2]

369

354

-4.1

2 6 . 4 K 2 0 " 73.6SiO2

[2]

337

340

0.9

162

M. Yamane, .I.D. Mackenzie, Vicker's hardness of glass

Table 2 (continued)
Ref.

Glass (mol %)
18Na20
18Na20
18Na20
18Na20
18Na20
18Na20
14Na20
10Na20

10BaO 72SIO2
10PbO 72SIO2
10MgO 72SIO2
10ZnO 72SIO2
10B203 72SIO2
10A1203 " 72SIO2
30PbO 56SIO2
50PbO 40SIO2

[2]
[2]
[2]
[2]
[2]
[2]
[2]
[2]

Hardness
measured
(kg/mm 2)

Hardness
calculated
(kg/mm 2)

Error
%

522
445
498
510
554
578
409
270

512
435
470
532
577
553
410
298

-1.9
-2.3
-5.6
4.3
4.1
-4.2
0.2
10.3

Substituting eqs. (18), (23)-(25) into eq. (11):

P { rNa
3 fNa + r 3 a f c a + r 3 i f s i + r ~ f o )
V = S4 7r/~r

(lla)

we obtain
V = 0.468.
Substituting the values from subsects. 4.1,4.2 and 4.3 into eq. (9), the hardness
number of 20Na20 10CaO 70SiO 2 glass is calculated as:
H v = 0.051(

0.583

-~1/2 7020
0.462 + 0.09 0.468 - 0.4682]

= 511 (kg/mm2).

(9a)

5. Comparison with experiment

The calculated values of hardness number from eq. (9) are compared with measured values for about 50 silicate glasses in table 2. The errors for most glasses are
less than 10%. Considering the uncertainty in the measured value o f hardness number and the assumptions underlying eq. (9), the agreement is very satisfactory.
For non-silicate glasses, there are insufficient data available to compare the calculated hardness numbers with measured values. Fig. 1 is the result of the comparison
for some simple glasses [4, 8, 10, 20] when the required parameters are available in
the literature [ 2 1 - 2 3 ] . The straight line represents a slope of unity. The agreement
between measured and calculated hardness is evident.

M. Yamane, J.D. Mackenzie, Vicker's hardness of glass

163

700

600
EE
E
~' 500

~Nap2Bp3
400
3oo

-~ 2oo

1oo

o6

/ As2Se5
I

100 200 300 400 500 600 700

,

Measured Hardness (Kglrnm 2)

Fig. 1. Agreement between measured values of Vicker's hardness and those calculated from
eq. (9) for some non-silicate glasses *.

6. Application to the development of hard glass

It has been shown that Vicker's hardness of silicate glass can be determined by
the average single bond strength, a, Young's modulus, E, and ionic volume fraction
V of the glass.
Among these parameters, however, the ionic volume fraction of most silicate
glasses are in the range from 0.4-0.55, and the effect of this factor is relatively
small compared to those of the other two. Thus glasses which are likely to have high
hardness numbers will be those containing oxides with a large value for Young's
modulus and strong bonds, such as BeO, A1203, La203, ZrO 2. This idea was tested
by preparing some glasses based on beryl frit with certain amounts of the above
oxides [24].
Beryl frit (SiO 2 64.73%, A1203 17.68%, BeO 11.94%, Fe203 0.94% and 4.7% of K,
Na, Li, Ca, Mg combined in weight) itself forms a glass of the Vicker's hardness number 750 kg/mm 2 (estimated value from eq. (9) is 800 kg/mm2). Hardness numbers
as high as 950 kg/mm 2 have been obtained this way [24].

Acknowledgements
The authors are grateful to the Chemical Sciences Directorate of AFOSR for the
support of this work under Grant No. 70-1856 and to Dr. A. Makishima for helpful
discussions.
* Hardness number for B2Oa was obtained by extrapolation in ref. [20].

164

M. Yamane, J.D. Mackenzie, Vicker's hardness of glass

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[21]
[22]
[23]
[24]
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