Mechanics of Supercooled Liquids

Pure substances can often be cooled below their melting points and still remain in the liquid state. For some supercooled liquids, a further cooling slows down viscous flow greatly, but does not slow down self-diffusion as much. We formulate a continuum theory that regards viscous flow and self-diffusion as concurrent, but distinct, processes. We generalize Newton's law of viscosity to relate stress, rate of deformation, and chemical potential. The self-diffusion flux is taken to be proportional to the gradient of chemical potential. The relative rate of viscous flow and self-diffusion defines a length, which, for some supercooled liquids, is much larger than the molecular dimension. A thermodynamic consideration leads to boundary conditions for a surface of liquid under the influence of applied traction and surface energy. We apply the theory to a cavity in a supercooled liquid and identify a transition. A large cavity shrinks by viscous flow, and a small cavity shrinks by self-diffusion.