Professional Documents
Culture Documents
392 Am. J. Phys. 66 ~5!, May 1998 © 1998 American Association of Physics Teachers 392
Table I. Typical compositions ~wt %! and VFT parametersa of window
glasses.
393 Am. J. Phys., Vol. 66, No. 5, May 1998 Edgar D. Zanotto 393
be calculated if one knows the viscoelastic functions—
relaxation modulus G(t) and the material compliance J(t).
An expression which relates G(t) and J(t) in the case of a
constant shear stress t 0 is given by
t 05 g~ 0 !G~ t !1 E t
0
G ~ t2t 8 !~ ] g / ] t 8 ! dt 8 , ~A3!
Thus
APPENDIX
1. Empirical theory of viscoelasticity
5
15 f ~ t ! 1 ~ G ` / h ! Ef 0
t
~ t2t 8 ! dt 8 1G ` Ef0
t
~ t2t 8 !
Assuming the Burgess model of viscoelasticity, let us
consider a creep experiment in which a constant shear stress 3@ ] h/ ] t 8 # dt 8 . ~A9!
t 0 is suddenly applied to a viscous liquid. The experimen- In the limit t→`, the first and third terms vanish, and
tally observed behavior of the deformation g (t) under con- therefore,
stant stress consists of three parts, schematically shown in
Fig. 2:
g ~ t ! / t 0 5 @ 1/G ` 1h ~ t ! 1t/ h # , ~A1!
h 5G ` Ef 0
`
~ t ! dt. ~A10!
where 1/G ` refers to the instantaneous elastic response ~seg- This is a rather extraordinary result, because the shear vis-
cosity can be determined simply as an integral over time of
ment AB in Fig. 2!, h(t) is the recoverable delayed elasticity
the stress relaxation function f (t).
@h(0)50, h(`)5constant, segment BC#, and the third term
Some insight can now be gained into Eq. (1):
refers to the irrecoverable viscous deformation ~segment
CD!. If the stress is suddenly released, instantaneous recov- h 5 ^ t & /C. ~A11!
ery occurs ~segment DE! followed by a relaxation period Then a comparison of Eqs. ~A10! and ~A11! show that
represented by segment EF and governed by the relaxation C51/G ` and
function f (t). The relaxation function is an intrinsic prop-
erty of the material under study. The right-hand side of Eq.
~A1! is defined as the compliance of the Burgess model,
^t&5 Ef0
`
~ t ! dt, ~A12!
J(t).
For long times, the elastic response and the delayed elas- so ^t& is the time average of the shear relaxation function!
ticity vanish, and thus
h5t0 /~ ]g/]t !, ~A2! 2. The free-volume model of viscosity
which defines the shear viscosity, h, for Newtonian fluids Most elements and compounds when molten have a vis-
such as oxide glasses. cosity about the same as that of water (1022 Pa s). On cool-
The change in time of some property of a glass, due to the ing the melt, crystallization occurs very rapidly a little below
imposed change of a variable ~temperature, stress, etc.! can the freezing point T f . There are, however, a few materials
394 Am. J. Phys., Vol. 66, No. 5, May 1998 Edgar D. Zanotto 394
material as a glass. The change from supercooled liquid to
glass, which may be considered as taking place at this tem-
perature, is not a sudden one, nor is T g a well-defined tem-
perature for any particular glass. Indeed the term ‘‘transfor-
mation range’’ is used more frequently than ‘‘transformation
temperature.’’ The temperature at which the change in slope
occurs is found to decrease as the rate of cooling is de-
creased. Also, if the glass is held at the temperature T, a little
below T g , its volume decreases slowly until it reaches a
point on the dotted line, which is an extrapolation of the
contraction curve of the supercooled liquid. The rate of
change of volume decreases as the dotted line is approached,
i.e., as the structure of the glass approaches an ‘‘equilib-
rium’’ configuration characteristic of the supercooled melt at
the temperature T. This equilibrium configuration has a
lower free energy than other liquidlike structures or configu-
Fig. 3. Relation between the glassy, liquid, and solid states. rations, but it is not, of course, that arrangement of molecules
which has the lowest possible free energy at the temperature
T ~the crystalline arrangement!. However, at temperatures
which form melts which are considerably more viscous. The significantly below T g , the rate at which the liquidlike glass
high viscosity indicates that the atoms or molecules in the structure can change is inversely proportional to the viscosity
melt are not so easily moved relative to one another by ap- and is very slow, as shown previously in this paper.
plied stresses. On cooling below the freezing point, crystal- Cohen and Turnbull10 developed a free-volume model of
lization does occur, but at a significantly lower rate than in viscous flow based on the idea that flow occurs by movement
the materials of the first group. The process of crystallization of molecules ~flow units! into voids of a size greater than
involves structural changes, i.e., the rearrangement of atoms some critical size. That is, the molecules rattle around in the
relative to one another. In simple terms, the relatively high cage created by surrounding molecules, until density fluctua-
viscosity of the melt and the low rate of crystallization are tions create a hole large enough for a molecule to jump into.
both consequences of the greater resistance to atomic rear- The free volume ( v f ) is somewhat vaguely defined, but it
rangement encountered in these materials. represents roughly the space not occupied by the core vol-
If the crystallization rate is low enough, it is possible to go
ume ( v 0 ) of the molecules. The viscosity can be written as
on cooling the melt below the freezing point without crystal-
lization taking place. As the melt cools, its viscosity contin- h 5 h 0 exp~ d v 0 / v f ! , ~A13!
ues to increase. This viscous liquid below the freezing point
is a supercooled liquid. Thus, strictly speaking, it is incorrect
to refer to it as a glass. Further cooling results in the viscos- v f / v 05 E
T0
T
~ a 1 2 a g ! dT 8 , ~A14!
ity rising to such a high value that the mechanical properties
of the material are closely similar to those of an ideal elastic where d is a constant close to unit, T 0 is the temperature
solid. The viscosity will then be at least 1012 – 1013 Pa s. This where v f 50, and a 1 and a g are the thermal expansion co-
solid material is a glass. efficients of supercooled liquid and glass, respectively
The volume–temperature diagram shown in Fig. 3 is use- ( a 1 . a g ), shown in Fig. 3. This equation reduces to the
ful in discussing the transformation from a supercooled liq- VFT equation if a 1 – a g is constant.
uid to a glass. If the melt crystallizes on cooling, this is
usually accompanied by a marked increase in density at the a!
Electronic mail: dedz@power.ufscar.br
melting point, T f . No such change occurs if the melt super- 1
Eduardo Mari, ‘‘Los mitos del vidrio,’’ Ceramica y Cristal 107, 29 ~1991!.
2
cools. The volume decreases along the line be. The decrease Michael Wysession, ‘‘The inner workings of the earth,’’ Am. Sci. 83,
in volume on cooling is due partly to the decreasing ampli- 134–147 ~1995!.
tude of atomic vibrations, and partly to changes in the struc-
3
W. O. Fellers, Materials Science, Testing and Properties ~Prentice-Hall,
Englewood Cliffs, NJ, 1990!, p. 204.
ture of the melt which result in it becoming more compact as 4
Encyclopedia Britannica—‘‘Viscosity’’ ~William Benton, Chicago, 1966!,
the temperature falls. At temperatures near T f these struc- Vol. 23, p. 198.
tural changes can occur very rapidly and will appear to occur 5
Steven Brawer, Relaxation in Viscous Liquids and Glasses ~American Ce-
instantaneously following any change in the temperature of ramic Society, Columbus, Ohio, 1985!, p. 24.
6
the material. As the viscosity increases with falling tempera- Narotan P. Bansal and Robert H. Doremus, Handbook of Glass Properties
~Academic, Orlando, 1986!.
ture, the structural changes occur increasingly slowly until 7
W. Muller, M. Torge, and K. Adam, ‘‘Ratio of CaO/K2O.2 as an evi-
eventually the viscosity becomes so high that no such further dence of a special Rheinish type of mediaeval stained glass,’’ Glastech.
changes are possible in laboratory time scales. A decrease in Ber.-Glass Science & Technology 67 ~2!, 45–48 ~1994!.
slope is then found in the V vs T curve ~point e!. With a 8
T. Lakatos, L.-G. Johansson, and B. Simmingskold, ‘‘Viscosity tempera-
further fall of temperature, the decreasing volume is due al- ture relations in the glass system SiO2-Al2O3-Na2O-K2O-CaO-MgO in the
most entirely to the decreasing amplitude of the atomic vi- composition range of technical glasses,’’ Glass Technology 13 ~2!, 88–95
~1972!.
brations. 9
Edgar D. Zanotto, ‘‘Isothermal and Adiabatic Nucleation in Glass,’’ J.
The temperature at which the change in slope occurs is Non-Cryst. Solids 89, 361–370 ~1987!.
called the transformation temperature or glass transition tem- 10
David Turnbull and Morrel Cohen, ‘‘On the free-volume model of the
perature, T g . Only below T g is it correct to describe the liquid-glass transition,’’ J. Chem. Phys. 52 ~6!, 3038 ~1970!.
395 Am. J. Phys., Vol. 66, No. 5, May 1998 Edgar D. Zanotto 395