See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/263558765

Viscosity activation energy

Article  in  Physics and Chemistry of Glasses · February 2007

CITATIONS READS

27 6,141

1 author:

Isak Avramov
Bulgarian Academy of Sciences
143 PUBLICATIONS   3,193 CITATIONS   

SEE PROFILE

All content following this page was uploaded by Isak Avramov on 26 May 2016.

The user has requested enhancement of the downloaded file.

 Phys. Chem. Glasses: Eur. J. Glass Sci. Technol. B, February 2007, 48 (1), 61–63

Viscosity activation energy

Isak Avramov
Institute of Physical Chemistry, 1113 Sofia, Bulgaria
Accepted 6 October 2006

The standard procedure of determining the activation energy for shear viscosity from the slope L of the Arrhenius plot,
lgη against 1/T leads frequently to overestimated values. The article discusses the significance of L and shows that an
important information can be retrieved from it value as the fragility parameter can be formulated as α=0·007Lg/Tg.
Fragility parameter α=1 is an indication for a strong glass with constant activation energy. It is demonstrated that the
average jump frequency model describes fairly the dependence of viscosity on chemical composition. On the contrary,
models based on mean activation energy considerations fail completely.

1. Introduction coordinates, logη against 1/T. In the high viscosity

Most of the models of shear viscosity assume that it is
a thermally activated process. To move, the molecules
have to overcome activation energy E(T) barriers(1)
created by the resistance of the surrounding building
units. Therefore, the jump frequency, is related to the
vibration frequency ν∞ according to equation
Ê E (T ) ˆ
n = n • exp Á -
Ë RT ˜¯
where R is the ideal gas constant. On the other hand,
viscosity η is related to the jump frequency ν of the
building units according to the Frenkel equation
RT 1
h=
3pVm n
where Vm is the molar volume. Maxwell gives an
alternative expression in the form
G•
h=
n
G∞ being the shear modulus. Therefore, viscosity is
also thermally activated
Ê E (T ) ˆ
h = h• exp Á
Ë RT ˜¯
There is a fundamental question: how to determine
experimentally the activation energy and how to
interpret it. Although the answer seems trivial, the
situation is quite tricky and misleading. The aim of
the present article is elucidate this problem.
2. Activation energies problem
The conventional procedure of determining the activa-
tion energy is to plot experimental data in Arrhenius
Email avramov@ipc.bas.bg
Physics and Chemistry of Glasses: European Journal of Glass Science and Technology Part B  Volume 48  Number 1  February 2007
region, experimental data give a straight line. There-
fore, a widespread fallacy is that the slope determines
directly the activation energy according to
1 E
L0 = (5)
2 ◊3 R
The provisional slope Lo, given by Equation (5),
(1) should be equal to the experimentally determined
slope L if the activation energy was constant. Since the
experimental data resemble a straight line, it seems
that this assumption is right. However, every curve
resemble to a straight line if the investigated interval
is sufficiently short (even the Equator looks like a
(2) straight line to the horizon limits). When viscosity
is studied in wider interval, the declination from
a straight line is becoming evident. The situation
is more complicated with relaxation experiments
because, in this case, it is much more difficult to
(3) widen the experimental interval. Hopefully, it was
proven(2–6) that relaxation process and shear viscos-
ity are controlled by the jump frequency of the same
building units, i.e. the relaxation time (reciprocal of
the jump frequency) is proportional to viscosity η. If
(4) the activation energy depends on temperature the
slope L is much larger the value of the provisional
slope L0
Ê ˆ
1 Á ∂ ˜
L = L0 + E (T )˜ (6)
2 ◊ 3RT Á ∂ 1
ÁË ˜¯
T
Unreasonably high values of E(T) are obtained if the
second term, in brackets, of Equation (6) is neglected.
At any temperature T, the absolute value of the acti-
vation energy can be determined from Equation (4)
provided the preexponential constant η∞ is estimated
properly. Taking into account typical values of the
shear modulus of glasses, the expected value is about
61

PC48_061-063 Avramov.indd 61 04/04/2007 12:29:59

 I. Avramov: Viscosity activation energy

logη∞≈−1. Earlier,(7) on the basis of experimental data Equation (12), is derived theoretically(7) within the
of more then 100 substances, we have demonstrated framework of the “jump frequency” model. A brief
that logη∞ varies in the limits −2≤logη∞≤1·5 [dPa s]. Let comparison between the “jump frequency” model
us determine the activation energy at temperature and the “average activation energy” models is given
Tg at which ηg=1013·5 [dPa s]. Equation (4) permits the in the Discussion part.
determination of the activation energy at Tg in the Equation (11) is based only on the assumption
following way that viscous flow is a thermally activated process.
Therefore, the definition of the dimensionless fra-
E(Tg)=2·3R(13·5−lgη∞)Tg=εRTg (7)
gility parameter α is universal. It accounts for the
where ε is a dimensionless constant having a value rate at which the activation energy changes with
hg E (Tg ) temperature. By means of Equations (5) and (6) α is
e = 2 ◊ 3 log = ª 32 ± 10% (8) expressed as follows
h• RTg
∂ ˘
Earlier, Bartenev has shown(8,9) that, for relaxation of E (T )˙
polymers ε≈31, i.e. this parameter is about the average
∂ (1/T ) ˚T =T
a = 1+ g
(13)
value reported here. With these considerations, the
activation energy for viscous flow is given by
( )
Tg E Tg
It is seen there is relationship between composition
E(Tg)=εRTg =265Tg±10% [J/mol] (9)
x and sensitivity of the activation energy to tempera-
In the literature, there is no unified definition ture changes in the corresponding glass transition
of the glass transition temperature. Here we adopt interval
ηg=1013·5 [dPa s] as a suitable definition of Tg. In ∂ ˘
this way Tg is always in the glass transition region E (T )˙
∂ (1 /T ) ˚T =T
and will coincide, within 2% of accuracy, with the
= 6x (14)
g

value determined according to other methods.

Additional advantage of this definition is that the
Tg E Tg ( )
relaxation time at this temperature is estimated to
be logτg≈2.
4. Discussion
The comparison of Equations (5) and (8) deter-
mines the provisional slope Lo as There are several models(7,10–12) capable of describ-
e ing the temperature dependence of viscosity with
L0 = Tg (10) sufficient accuracy. To distinguish which of them is
2 ◊3
better one has to test their possibility to describe with
The dimensionless ratio α no new assumptions, or new adjustable parameters,

a=
( ) = 2 ◊3 L
L Tg g
ª 0 ◊ 07
Lg
± 10% (11)
the dependence of viscosity on other chemical com-
position. Here we discuss viscosity of SiO2, when
L (T )
0 g
eT g Tg low concentration of modifying oxides is added. In
this case, a tiny fraction Qi(x) of the SiO4 tetrahedra
is a measure of the “fragility” of the system. In other is expected to have i broken Si–O–Si bridges (i varies
words, it determines how fast the activation energy between 1 and 4). Detailed investigation on Qi(x) is
is changing with temperature. In Equation (11) Lg given in Ref. 13
stands for slope at the glass transition temperature, 4!
Lg≡L(Tg). Qi = (1 - p)4- i pi (15)
i ! ( 4 - i )!
The mobility of SiO4 tetrahedra is connected with
3. Influence of chemical composition on
much lower activation energy in the presence of
viscosity
broken bridges. If E0 is the activation energy of SiO4
Data on fragility α on more then 100 substances tetrahedra with no broken bonds and Ei(T) is the
are summarised in Ref. 7. It was shown experimen- corresponding value of SiO4 tetrahedra with i broken
tally (for alkaline and for most of the alkaline earth bonds, the average activation energy is given ap-
silicates), that α depends on composition x in the proximately as follows
following way 4

α(x)=1+6x (12)
E = ÂQ (x) E (T )
i=0
i i (16)

The chemical composition is expressed by the molar It is seen that at low concentrations of the modifying
fraction x of the modifying oxides, respectively, oxides the average value of the activation energy
1−x is the molar fraction of SiO2. The same result, remains almost unchanged. However, experimental
62  Physics and Chemistry of Glasses: European Journal of Glass Science and Technology Part B  Volume 48  Number 1  February 2007

PC48_061-063 Avramov.indd 62 04/04/2007 12:30:01

 I. Avramov: Viscosity activation energy
H
Figure 1. Dependence of the viscosity on composition at
1473 K. Solid line is according to the jump frequency model
while the dotted line is according to the mean activation
energy approach. The parameters used are as follows:
Eo=380 kJ/mol; Ei=Ei−1/2, i=1 to 4. The solid points are
experimental results from Refs 14–18
data(14–18) show that viscosity drops fast as illustrated
by the solid points in Figure 1. It gives viscosity at
1473 K in dependence of the molar fraction x of the
modifying oxides. Most of the approaches are based
on sophisticated models determining the average
activation energy <E>. Afterwards, the viscosity is
determined by introducing the value of <E> into
Equation (4). The result is illustrated by a dotted
line in Figure 1. The complete failure of the “average
energy” models is evident. Once the effective activa-
tion energy E0 for motion of SiO4 tetrahedra with no
broken bond is fixed, it is not possible to find a set of
Ei values suitable to describe the experimental data
by means of <E> models.
The alternative approach (see Refs 7,13,19) is first
to determine the mean jump frequency <ν> accord-
ing to
4 12. Adam, G. & Gibbs, J. J. Chem. Phys., 1965, 43, 139.
n = ÂQ (x)n (T )
i=0
i i
(17)
where the jump frequencies νi(T) are determined by
the corresponding activation energies Ei according to
Equation (1). Than viscosity is determined by intro-
ducing the average jump frequency <ν> in Equation
(2) (or alternatively in Equation (3)). It is seen that the
mean jump frequency is not determined by the mean
the activation energy, i.e. <ν>≠ν∞ exp(−<E>/RT). The
Physics and Chemistry of Glasses: European Journal of Glass Science and Technology Part B  Volume 48  Number 1  February 2007
PC48_061-063 Avramov.indd
View publication stats 63
solid line in Figure 1 is drawn according to Equation
(17), for Ei≈Ei−1/2. The same values are applied in cal-
culating the dotted line according to <E> model. The
superior accuracy of the jump frequency approach
is readily seen.
5. Conclusions
It is fallacious to determine the activation energy E(T)
from the slope L of the Arrhenius plot of viscosity
against reciprocal temperature. In the glass transition
interval the slope Lg plays an important role as the
ratio α=0·07(Lg/Tg)±10% determines the “fragility”
parameter, indicating the sensibility of the activation
energy on temperature. In other words, determining
how “short” is the glass.
There is a strong experimental indication that the
average jump frequency model is capable to describe
with superior accuracy viscosity as compared to the
mean activation energy approaches.
Acknowledgment
The author appreciates support of the Project IN-
TERCONY.
References
1. Glasstone, S., Laider, H. & Eyring, H. The Theory of Rate Processes.
Princeton Univ. Press , New York. London, 1941.
2. Moynihan, C. T., Easteal, A. J. & DeBolt, M. A. J. Am. Ceram. Soc., 1976,
59, (1976) 12.
3. Moynihan, C. T., Easteal, A. J. & DeBolt, M. A. J. Am. Ceram. Soc., 1971,
54, 491.
4. Avramov, I., Grantscharova, E. & Gutzow, I. J. Non-Cryst. Solids, 1987,
91, 386.
5. Scherer, G. in "Glass 89" Proc. XV Int. Congr. on Glass, Leningrad, 1989,
p.254.
6. Mazurin, O. V. J. Non-Cryst. Sol., 1977, 25, 130.
7. Avramov, I. J. Non-Cryst. Solids., 2005, 351,3163.
8. Bartenev, G. Structure and Mechanical Properties of Inorganic Glasses (in
Russian). Moskow: Lit. po Stroitelstvu, 1966.
9. Bartenev, D. Sanditov, Dokl. Acad. Nauk SSSR, 1989, 304, 1378.
10. Cohen, M. & Turnbull, D. J. Chem. Phys., 1970, 52, 3038.
11. Macedo, P. & Litovitz, T. J. Chem. Phys., 1963, 42, 245.
13. Avramov, I., Rüssel, C. & Keding, R. J. Non-Cryst. Solids, 2003, 324,
29.
14. Buckermann, W.-A., Müller-Warmuth, W. & Frischat, G. H. Glastech.
Ber., 1992, 65, 18.
15. Stebbins, J. F. J. Non-Cryst. Solids, 1988, 106, 359.
16. Emerson, J. F., Stallworth, P. E. & Bray, P. J. J. Non-Cryst. Solids, 1989,
113, 253.
17. Mazurin, O., Streltsina, M. & Shvaiko-Shvaikovskaya, T. Handbook of
Glass Data, Elsevier, Amsterdam, 1983.
18. Partington, J. An advanced treatise of physical chemistry, Vol. 3, Longmans,
London, New York, Toronto, 1957, p. 367.
19. Avramov, I. J. Non-Cryst. Solids, 2000, 262, 258.
63
04/04/2007 12:30:01