TY - JOUR

T1 - The rheology of solid glass

AU - Williams, Stephen R.

AU - Evans, Denis J.

PY - 2010

Y1 - 2010

N2 - As the glass transition is approached from the high temperature side, viewed as a liquid, the properties of the ever more viscous supercooled liquid are continuous functions of temperature and pressure. The point at which we decide to classify the fluid as a solid is therefore subjective. This subjective decision does, however, have discontinuous consequences for how we determine the rheological properties of the glass. We apply the recently discovered relaxation theorem to the time independent, nondissipative, nonergodic glassy state to derive an expression for the phase space distribution of an ensemble of glass samples. This distribution is then used to construct a time dependent linear response theory for aged glassy solids. The theory is verified using molecular dynamics simulations of oscillatory shear for a realistic model glass former with excellent agreement being obtained between the response theory calculations and direct nonequilibrium molecular dynamics calculations. Our numerical results confirm that unlike all the fluid states, including supercooled liquids, a solid glass (in common with crystalline states) has a nonzero value for the zero frequency shear modulus. Of all the states of matter, a supercooled fluid approaching the glass transition has the highest value for the limiting zero frequency shear viscosity. Finally, solid glasses like dilute gases and crystals have a positive temperature coefficient for the shear viscosity whereas supercooled and normal liquids have a negative temperature coefficient.

AB - As the glass transition is approached from the high temperature side, viewed as a liquid, the properties of the ever more viscous supercooled liquid are continuous functions of temperature and pressure. The point at which we decide to classify the fluid as a solid is therefore subjective. This subjective decision does, however, have discontinuous consequences for how we determine the rheological properties of the glass. We apply the recently discovered relaxation theorem to the time independent, nondissipative, nonergodic glassy state to derive an expression for the phase space distribution of an ensemble of glass samples. This distribution is then used to construct a time dependent linear response theory for aged glassy solids. The theory is verified using molecular dynamics simulations of oscillatory shear for a realistic model glass former with excellent agreement being obtained between the response theory calculations and direct nonequilibrium molecular dynamics calculations. Our numerical results confirm that unlike all the fluid states, including supercooled liquids, a solid glass (in common with crystalline states) has a nonzero value for the zero frequency shear modulus. Of all the states of matter, a supercooled fluid approaching the glass transition has the highest value for the limiting zero frequency shear viscosity. Finally, solid glasses like dilute gases and crystals have a positive temperature coefficient for the shear viscosity whereas supercooled and normal liquids have a negative temperature coefficient.

UR - http://www.scopus.com/inward/record.url?scp=77952702137&partnerID=8YFLogxK

U2 - 10.1063/1.3418442

DO - 10.1063/1.3418442

M3 - Article

SN - 0021-9606

VL - 132

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 18

M1 - 184105

ER -