Hostname: page-component-5c6d5d7d68-vt8vv Total loading time: 0.001 Render date: 2024-08-08T05:33:39.865Z Has data issue: false hasContentIssue false

A Relation Between Fragility, Specific Heat, and Shear Modulus Temperature Dependence for Simple Supercooled Liquids

Published online by Cambridge University Press:  10 February 2011

A. V. Granato*
Affiliation:
University of Illinois, Dept. of Physics, Urbana, IL 61801, granato@uiuc.edu
Get access

Abstract

It is often said that the fragility and specific heat discontinuity at the glass transition are related characteristic features of glasses. We give a relation between these quantities for simple liquids, and also find that the temperature dependence of the shear modulus should be closely related to these quantities. According to the Interstitialcy Theory, the liquid state shear modulus G = Go, exp (-βc) = Go exp {-γ[(T/To)-l ]}, where Gois the shear modulus at a reference temperature To, which can be taken to be the glass temperature. In these relations, βis the diaelastic shear susceptibility, c is the interstitialcy concentration, T is the temperature, and dc/dT = γ/βTo. It has been proposed by Dyre, Olsen and Christensen that U in the viscosity η = ηo exp (U/kT) be given as the work done in shoving aside particles during a diffusion step, and therefore be proportional to the (liquid state) shear modulus. If so, then combining the above relations, the fragility F = [d log η/d (Tg/T]T=Tg becomes F=(1+γ) log [η (Tg)/ηo], where γ = - (Tg/G)(dG/dT). Then, since δCv, = UF(dc/dT), where UF is the interstitialcy formation energy, one obtains further with reasonable simplifying approximations δCv/Cv∼γG(T)/Goo, where Goo is the zero temperature crystalline shear modulus. For a typical fragile glass γ ∼ 2 (F ∼ 50) with G(Tg)/Goo ∼ 1/2, then δCv/Cv, ⊼ 1, ut close to zero for strong glasses, in fair agreement with available experimental results. The perspective given by the Interstititialcy Theory is then that the fragility is given phenomenologically by the temperature dependence of the shear modulus, or microscopically by the rate of increase of the equilibrium interstitialcy concentration with temperature.

Type
Research Article
Copyright
Copyright © Materials Research Society 1999

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1. Angell, C.A., in Relaxation in Complex Systems, Ngai, K. and Wight, G.B., Eds. (National Technical Information Service, U.S. Department of Commerce, Springfield, VA, 1985) p. 111.Google Scholar
2. Granato, A.V., Phys. Rev. Lett. 68, p. 974977, (1992).Google Scholar
3. Granato, A.V., Met. and Mat. Trans. A, 29A, p. 18371843 (1998).Google Scholar
4. Dyre, J.E., Olsen, N.B. and Christensen, T., Phys. Rev. B53, p. 2171 (1996).Google Scholar
5. Zhu, D.M. and Chen, H., J. Non-Cryst. Sol., 224, p. 97101 (1998).Google Scholar
6. Plazek, D.J. and Ngai, K.L., Macromolecular 24, p. 1222 (1991).Google Scholar
7. Bohmer, R., Ngai, K.L., Angell, C.A. and Plazek, D.J., J. Chem. Phys. 99, p. 42014209 (1993).Google Scholar
8. Barlow, A.J., Lamb, J., Matheson, A.J., Padmini, P.R.K.L., and Richter, J., Proc. Roy. Soc. London Ser. 1298, pp. 467480 (1967).Google Scholar