Journal of Molecular Structure 993 (2011) 155159

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Journal of Molecular Structure

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Temperature dependence of elastic properties in alkali borate binary glasses

Mitsuru Kawashima, Yu Matsuda 1, Seiji Kojima
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8573, Japan

a r t i c l e

i n f o

Article history:
Available online 12 November 2010
Keywords:
Alkali borate glass
Elastic property
Glass transition
Fragility
Relaxation
Brillouin scattering

a b s t r a c t
The elastic properties of alkali borate glasses, xM2O(100  x)B2O3 (M = Li, Na, K, Rb, Cs, x = 14, 28), have
been investigated by Brillouin scattering spectroscopy from room temperature up to 1100 C. Above the
glass transition temperature, Tg, the longitudinal sound velocity, VL, decreases markedly on heating. Such
signicant changes of the elastic properties result from the breakdown of the glass network above Tg.
Alkali borate family with the same x shows the similar behavior in the temperature variations of VL up
to around Tg. The absorption coefcient, aL, increases gradually above Tg. With the increase of the size
of an alkali ion, the slope of VL just above Tg decreases. Since the fragility is related to the slope, the present results suggest that the fragility of alkali borate glasses increases as the size of alkali ion decreases.
Such an alkali dependence of the fragility is discussed on the basis of the uctuation of the boron coordination number.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Pure B2O3 glass has a random three-dimensional network of
BO3 triangles with a large fraction of almost planar B3O6 boroxol
rings. It is known that alkali borate glasses show the anomalous
composition dependences of physical properties, such as density
[1], sound velocity [2,3] and thermal expansion [4], by the addition
of alkali oxide to pure B2O3 glass. Previous studies reported that
the structural origins of such anomalies are strongly related to
the change of the boron coordination number from three to four
and the formation of non-bridging oxygen [5]. The fourfold coordinated boron atoms enhance the network rigidity by the crosslinking of borate framework. In contrast, the non-bridging oxygen
destroys the borate network. The negative charge of the network
sites is compensated by the positive charge of alkali ions, M+. The
alkali ions do not directly participate in the network formation
and occupy interstitial voids. As a consequence, the structures of
modied borate glasses are essentially built up from the covalently
bonded structural units. While, the ionic bonds are formed between M+ and the BO anionic units, and their bond strength depends on the specic alkaline cation. The studies by nuclear
magnetic resonance (NMR) [5] and Raman scattering measurement
[6] show that the fraction of fourfold coordinated boron atoms of
alkali borate glasses decreases as the size of an alkali ion increases
at room temperature. This fact indicates that the preference large
alkalis induce the creation of non-bridging oxygen. Therefore, for
Corresponding author. Tel.: +81 29 8535307; fax: +81 29 8534490.
E-mail address: kojima@bk.tsukuba.ac.jp (S. Kojima).
Present address: Glass Research Center, Central Glass Co. Ltd., Matsusaka, Mie 5150001, Japan.
1

0022-2860/$ - see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2010.11.006

the same alkali composition, the sound velocity and elastic moduli
increase as the size of an alkali ion decreases.
The elastic properties far below a glass transition temperature,
Tg, are relatively stable in comparison with the temperature variation above Tg. In contrast, the breakdown of the network starts
above Tg. The breakdown of the structural integrity is reected in
the rapid decrease of the rigidity. The network rigidity is directly
connected to the structural (a) relaxation process characterized
by the Angells fragility. Therefore, to make clear the mechanism
of a glass transition and the nature of supercooled liquid, it is necessary to clarify the elastic properties over a wide temperature
range. Moreover, the understanding of elastic properties at high
temperatures is very important for the glass manufacturing
process.
In this study, we employ Brillouin scattering spectroscopy to
measure elastic properties at high temperatures up to 1100 C.
Although the non-destructive and non-contact Brillouin scattering
is a powerful tool to investigate the elastic properties at high temperatures, only a few investigations were reported until now on
elastic properties of alkali borate glasses above Tg using Brillouin
scattering. Masnik et al. showed the temperature dependences of
longitudinal elastic modulus of sodium borate glasses and discussed a relaxation process above Tg in the GHz frequency region
[7]. Ike et al. reported the temperature dependences of the elastic
properties of lithium borate glasses [8]. Since their results focus on
the effect of temperature and composition dependences, the inuence of an alkali ion and alkali dependence of fragility were not
sufciently discussed. In this study, the temperature dependence
of elastic properties in alkali borate glasses xM2O(100  x)B2O3
(M = Li, Na, K, Rb, Cs, x = 14, 28), where x denotes the molar composition (mol%), are investigated by Brillouin scattering up to

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M. Kawashima et al. / Journal of Molecular Structure 993 (2011) 155159

1100 C. The inuence of alkali cations to the temperature dependence of the elastic properties and the variation of fragility are
discussed.

samples were determined from Brillouin shift, Dm180, and FWHM,

C, using the following equations:

VL

Dm180 k
;
2n sinh=2

2. Experimental
xM2O(100  x)B2O3 (M = Li, Na, K, Rb, Cs, x = 14, 28) glasses were
prepared by the solution method [9]. This method is useful to obtain
the high homogeneity of glasses. Analytical-reagent-grade MOH and
H3BO3, starting materials, were reacted in an aqueous solution to
achieve the high homogeneity. Then the mixed solution was transferred to a dry box and after the complete evaporation of water a
chemically synthesized powder was obtained. The powder was
melted in a furnace at 1000 C, and then the melt was quenched by
pressing between two aluminum plates. The actual compositions
of all samples were analyzed with respect to both x and (100  x)
by the potentiometric titration chemical analysis [10].
The experimental setup of a Brillouin scattering apparatus is
described elsewhere [8]. The features of this system are the combination of an optical microscope (Olympus BH-2) and a Sandercocktype 3 + 3 passes tandem multipass FabryPerot interferometer.
The Brillouin scattering spectra were measured at a backward scattering geometry. A standard photon counting system and a multichannel analyzer were used to accumulate the signals. To measure
the spectra at high temperatures up to 1100 C, we prepared the
compact IR image furnace (Yonekura, IR-TP) specially customized
for the present experiments. The combination of Brillouin apparatus and the compact IR image furnace enable us to prove elastic
properties over a wide temperature range.

aL

pC
VL

where n is the refractive index, k is the wavelength of the incident

beam (532 nm) and h is the scattering angle (180). The values of n
for each sample are taken from the data of Refs. [11,12]. Since the
values are available only at room temperature, it is assumed that
the change of n is much smaller than that of Brillouin shifts.
Fig. 2a and b shows temperature dependences of VL and aL in
14M2O86B2O3 glass. Fig. 3a and b shows those of 28M2O72B2O3
glass. Such temperature dependences are commonly observed for
glass-forming liquids [13,14]. Each VL decreases very rapidly above
an inection point between 300 C and 400 C. This characteristic
inection point can be identied as Tg. In the case of strong pure
SiO2 glass, the elastic properties exhibit a monotonous increase on
heating even above Tg [15]. The anomaly near Tg is remarkable in
fragile alkali borate glasses of which anharmonicity are much
stronger than that of pure SiO2 glass. At room temperature, VL increases as the size of an alkali ion decreases. The fraction of fourfold coordinated boron atoms at the same alkali composition
becomes large as the size of an alkali ion decreases [5]. The fourfold
boron atoms increase the network rigidity by the cross-linking of
borate framework with the covalent BO bonds, and subsequently
yields higher Tg. Therefore, the inection point (Tg) shifts become
higher temperature as the size of an alkali ion decreases. While,

3. Results and discussion

(a)

5500

Sound velocity VL (m/s)

3.1. Temperature dependence of elastic property of alkali borate

glasses
The temperature dependence of Brillouin spectra of 28Rb2O
72B2O3 glass is shown in Fig. 1. The observed spectrum contains
a longitudinal acoustic (LA) mode and a central peak. The Brillouin
shift of a LA mode decreases on heating. The central peak appears
above 700 C, and its intensity increases on further heating. The
central peak was observed in all samples at high temperatures,
and its intensity increases as the size of an alkali ion decreases.
These Brillouin spectra were analyzed by convoluting a Lorentzian spectral function with a Gaussian broadening function. The longitudinal sound velocity, VL, and absorption coefcient, aL, of the

14LiB
14NaB
14KB
14RbB
14CsB

5000
4500
4000
3500
3000
2500
2000

200

400

600

800

1000

1200

Temperature ( C)

(b)
900 C
o

800 C
o

700 C
o

450 C
o

250 C
o

25 C
-20

20

Brillouin shift (GHz)

Fig. 1. Temperature dependence of Brillouin spectra of 28Cs2O72B2O3 glass,
measured at backward scattering geometry. LA and CP denote the longitudinal
acoustic phonon and central peak, respectively.

-1

Absorption coefficient (m )

Scattering intensity (arb. unit)

6x10
-1

LA
CP

Absorption coefficient L (m )

28Rb2O-72B2O3

5x10

4x10

3x10

6x10

5x10

4x10

3x10

2x10

1x10
0

200

400

600

800 1000 1200

o

Temperature ( C)

2x10

14LiB
14NaB
14KB
14RbB
14CsB

1x10

0
0

200

400

600

800

1000

1200

Temperature ( C)
Fig. 2. Temperature dependences of (a) longitudinal sound velocities and (b)
absorption coefcients of 14M2O86B2O3 glasses. Inset of (b): tting curve of the
quadratic form.

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M. Kawashima et al. / Journal of Molecular Structure 993 (2011) 155159

28LiB
28NaB
28KB
28RbB
28CsB

6000
5000
4000
3000
2000
0

200

400

600

800

1000

1200

Temperature ( C)

8.0x10

6.0x10

-1

1.0x10

Absorption coefficient (m )

-1

Absorption coefficient L (m )

(b)

fraction at the ring position [21]. As a result, the glass network is

broken and random connections of BO3 triangular units are formed
at high temperatures. Therefore, the glass network above Tg is broken by the creation of random connections and non-bridging oxygen. However, the extent of connectivity in glass network remains
unchanged from room temperature up to Tg. Consequently, below
Tg, the changes of VL and absorption coefcient are very small,
whereas above Tg, their changes are drastic.
The aL gradually increases from Tg to the highest temperature
observed. Since the random connections and the non-bridging oxygen loosely connect to the network, they induce the energy dissipation of the elastic wave propagation and the increase of the
damping of the sound wave. Both temperature dependences of aL
of x = 14 and 28 mol% do not depend on the size of an alkali ion,
and show the similar behavior from room temperature up to about
850 C. In this temperature region, the temperature dependence of
aL is tted by the quadratic form for both compositions.

1.0x10

8.0x10

aL T 7:5  T  3502 275; 000 x 14 mol%;

aL T 14:8  T  3502 275; 000 x 28 mol%:

6.0x10

4.0x10

2.0x10

0.0

4.0x10

200

400

600

800 1000 1200

o

Temperature ( C)

28LiB
28NaB
28KB
28RbB
28CsB

2.0x10

0.0

200

400

600

800

1000

1200

Temperature ( C)
Fig. 3. Temperature dependences of (a) longitudinal sound velocities and (b)
absorption coefcients of 28M2O72B2O3 glasses. Inset of (b): tting curve of the
quadratic form.

with the increase of the size of an alkali ion, the fraction of fourfold
coordinated boron atoms decreases and the number of the nonbridging oxygen increases at the same alkali composition. Since a
non-bridging oxygen atom connects to an alkali ion by an ionic
bond, its strength strictly depends on the alkali ion size. Moreover,
the study of molecular dynamics simulation showed that small alkali ions can enter into the matrix of pure B2O3 glass without
inducing large modications of the borate network, and when
the other alkali ions are added to the initial structure, the network
opens to accommodate the larger size of the cation [16]. Thus, the
loose structure increases with the increase of the alkali size.
Above Tg, each VL decreases very rapidly. Such sudden decrease
at Tg in Figs. 2a and 3a indicates that the structure of the glass network becomes weaker above Tg. This drastic change is caused by
the breakdown of the glass network. The decrease of the fraction
of the fourfold coordinated boron atoms on heating above Tg has
been also conrmed by the neutron diffraction study [17]. The
fourfold coordinated boron atoms are converted to the threefold
coordinated boron atoms. Such decrease of the boron coordination
number induces a partial decomposition of the network above Tg
through the formation of non-bridging oxygen. Therefore, heating
causes the decrease of the boron coordination number, resulting
in the creation of the planar weak structural units and non-bridging oxygen. Indeed, a molecular dynamics simulation of lithium
borate glasses also found that the number of non-bridging oxygen
in the vicinity of a Li ion increases on heating [18]. Moreover, the
Raman scattering study of alkali borate glasses revealed that the
concentration of boroxol rings rapidly decreases above Tg owing
to the opening of boroxol rings [19,20]. Similarly, the NMR study
on sodium borate glasses have shown the decrease of the boron

These tting results are shown in the insets of Figs. 2b and 3b. Temperature dependence of aL of x = 28 mol% rises more rapidly than
that of x = 14 mol% above Tg. In high temperatures, the aL becomes
larger as the size of an alkali ion decreases.
3.2. Scaled sound velocity
The temperature dependences of VL shown in Figs. 2a and 3a
were scaled in such a way that VL and T are scaled by VL at Tg
and Tg, respectively. Figs. 4 and 5 show the scaled temperature
dependences of VL. Despite the decrease of VL at room temperature
with the alkali ion size, these dependences were clearly scaled in
the same alkali composition from room temperature up to Tg. In
contrast, the scaled composition variation of its temperature
dependence of potassium borate glasses [22] cannot fall into the
master curve as shown in Fig. 6. Therefore, in the same alkali composition, the variations of structure with temperature up to around
Tg obeys the similar mechanism, while, in the different composition, the different temperature variations were observed. This
means that the glass network at this temperature range is essentially constructed by the boron and oxide atoms, and the inuence
of alkali ions is small. While, at high temperatures the inuence of
alkali ions becomes larger.

1.1

14LiB
14NaB
14KB
14RbB
14CsB

1.0
0.9
Tg

Sound velocity VL (m/s)

7000

VL/VL

(a)

0.8
0.7
0.6
0.5

T/Tg
Fig. 4. Scaled temperature dependence of VL of 14M2O86B2O3 glasses in such a way
that VL and T are scaled by VL at Tg and Tg, respectively.

M. Kawashima et al. / Journal of Molecular Structure 993 (2011) 155159

1.0

VL/VL

Tg

0.9
0.8

28LiB
28NaB
28KB
28RbB
28CsB

0.7
0.6
0.5
0.4
0

T/Tg
Fig. 5. Scaled temperature dependence of VL of 28M2O72B2O3 glasses in such a way
that VL and T are scaled by VL at Tg and Tg, respectively.

VL scaled by VL at Tg

1.1

xK 2O(100-x)B2O3

1.0
0.9
0.8

x=4
x = 10
x = 14
x = 20
x = 28
x = 34

0.7
0.6
0.5
0.4

T/Tg
Fig. 6. Scaled temperature dependence of VL of xK2O(100  x)B2O3 glasses (x = 4,
10, 14, 20, 28, 34 mol%) in such a way that VL and T are scaled by VL at Tg and Tg,
respectively.

3.3. Fragility of alkali borate glasses

Angell has proposed a useful measure of the classication of
glass-forming materials on the basis of the temperature dependence of viscosity or structural relaxation time, using the concept
of strong and fragile liquids [23]. For a strong liquid, the temperature dependence of the characteristic relaxation time follows
an Arrhenius behavior. While, the characteristic relaxation time
of fragile liquid changes rapidly with super-Arrhenius temperature
dependence and follows a Vogel-Fulcher behavior. The fragility is
dened from the dependence of log g on Tg/T and, the degree of
the fragility is evaluated quantitatively by steepness index m



 d log s 
:
m lim 
T!T g dT=T 

of dVL/dT just above Tg is shown in Fig. 7, where open symbols denote fragility indices of lithium (square) and sodium (circle) borate
glasses reported in Ref. [24], respectively. As can be seen in Fig. 7,
dVL/dT just above Tg of alkali borate glasses increases with the increase of the alkali composition. The alkali dependence of fragility
indicates that the fragility of alkali borate glasses increases with
the decrease of the size of an alkali ion, especially the fragility of
28M2O72B2O3 shows a remarkable alkali dependence. Chryssikos
et al. suggested that lithium borate glass is more fragile than sodium borate glass from both the viscosity and specic heat data
[26]. Our result is in agreement with their suggestion, and not only
lithium and sodium borate glasses but also potassium, rubidium,
and cesium borate glasses show the alkali dependence of fragility.
Even the changes in the cation network interactions is modest,
they have a signicant impact on a glass transition.
Vilgis proposed the theoretical model on the fragility to understand the mechanism of glass-forming liquids near Tg [27,28]. The
summary of the model is that a degree of the fragility relates to a
degree of the uctuation of the coordination number. For instance,
vitreous silica SiO2 belongs to the strong since it has a xed covalent bonding of Si atom, which is four-coordinated to oxygen
atoms. While, ortho-terphenyl (OTP), one of the well-known
molecular glass-formers, belongs to the typical fragile one since
its coordination number uctuates from 11 to 16 [28], indicating
that the molecules interact with each other cooperatively. In the
case of alkali borate glasses, the coordination number of a boron
atom changes from three to four by the addition of alkali oxide.
Therefore, as the fraction of fourfold coordinated boron atoms N4
approaches 0.5, the uctuation of the boron coordination number
increases. Matsuda et al. experimentally revealed the correlation
between the fragility and the uctuation of the boron coordination
number in lithium borate glasses over a wide composition range
[29]. Zhong and Bray showed that N4 in alkali borate glass decreases in the order of Li, Na, K, Rb, Cs; also, the value of the x,
for which N4 exhibits a maximum, decreases with the increase of
the size of an alkali ion [5]. The N4 of lithium borate glass, which
is the highest in the same alkali compositions, exhibits a maximum, N4 = 0.4, at x = 40 mol%. From the alkali dependence of N4,
the uctuation of the boron coordination number decreases with
the increase of the size of an alkali ion. Thus, the uctuation in lithium borate glass is the highest and the uctuation of cesium borate
glass is the lowest in the same composition. Therefore, the Vilgis
model predicts that the fragility of alkali borate glasses increases
with the increase of the alkali composition up to at least
x = 28 mol% and decreases with the increase of the size of an alkali
ion. In Fig. 7, this suggestion is in agreement with the behavior of

xM2O(100-x)B2O3

In alkali borate glasses, it is known that the addition of alkali oxide

to pure B2O3 glass causes a marked change of fragility from strong
to fragile [24].
The slope of the decrease in VL at Tg in Figs. 2a and 3a is a direct
measure of the structural degradation of glass-forming liquids, because the Brillouin scattering technique can probe the structural
relaxation in the GHz frequency range. This slope in VL at Tg can
be used as a measure of fragility [7,25]. Very recently, we have
shown that the slope of VL just above Tg of potassium borate glass
increases with the increase of the K2O composition as well as the
composition dependence of the fragility in Ref. [22]. The rate in
Figs. 2a and 3a is more rapid with the decrease of the size of an alkali ion. Above Tg, VL decreases very rapidly. The alkali dependence

70

[24]

Fragility index of M = Li
[24]
Fragility index of M = Na
M = Li
M = Na
M=K
M = Rb
M = Cs

60

50

Fragility index m

1.1

dVL/dT

158

40

14

28

30

Alkali composition (mol%)

Fig. 7. Alkali dependence of dVL/dT of xM2O(100  x)B2O3 glasses (M = Li, Na, K, Rb,
Cs, and x = 14, 28) just above Tg. Open symbols denote fragility indices of lithium
(square) and sodium (circle) borate glass reported in Ref. [24]. The increase of
fragility means the glasses become fragile. While, the decrease of fragility means
the glasses become strong.

M. Kawashima et al. / Journal of Molecular Structure 993 (2011) 155159

the slope of VL just above Tg. In other words, the increase of the
composition and the decrease of the alkali ion size induce fragile,
whereas, the decrease of the composition and the increase of the
alkali ion size induce strong. The fragility of 28M2O72B2O3 glass
is expected to show the composition dependence more remarkable
than that of 14M2O86B2O3 glass, because the difference of the formation of the four-coordinated boron atoms by alkali oxide becomes signicant with the increase of the alkali composition
[5,30]. The prediction by Vilgis enables us to explain the alkali
dependence of the fragility estimated in the present work. In alkali
borate glasses, the origin of fragility strongly correlates to the formation of the four-coordinated boron atoms.
4. Conclusions
At room temperature, VL of alkali borate glasses increases as the
size of alkali ion decreases. From room temperature to Tg, the extents of the connectivity in the glass network remain unchanged.
In this temperature region, the glass network is almost constructed
by the boron and oxide atoms independent of the inuence of alkali ions. In contrast, above Tg, since the glass network is completely
disintegrated, random connections and non-bridging oxygen are
created. Therefore, VL of alkali borate glasses decreases drastically
and aL increases with the increase of temperature. It is found that
the fragility of alkali borate glasses increases as the size of an alkali
ion decreases. The observed result is consistent with the prediction
by the Vilgis model. The formation of the four-coordinated boron
atom plays the dominate role in the fragility of the borate glass
system.
Acknowledgement
One of the authors (Y.M.) is thankful for the JSPS Research Fellowship 19-574.

159

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