  Simulations are used to examine the microscopic origins of strain hardening
in polymer glasses. While stress-strain curves for a wide range of temperature
can be fit to the functional form predicted by entropic network models, many
other results are fundamentally inconsistent with the physical picture
underlying these models. Stresses are too large to be entropic and have the
wrong trend with temperature. The most dramatic hardening at large strains
reflects increases in energy as chains are pulled taut between entanglements
rather than a change in entropy. A weak entropic stress is only observed in
shape recovery of deformed samples when heated above the glass transition.
While short chains do not form an entangled network, they exhibit partial shape
recovery, orientation, and strain hardening. Stresses for all chain lengths
collapse when plotted against a microscopic measure of chain stretching rather
than the macroscopic stretch. The thermal contribution to the stress is
directly proportional to the rate of plasticity as measured by breaking and
reforming of interchain bonds. These observations suggest that the correct
microscopic theory of strain hardening should be based on glassy state physics
rather than rubber elasticity.
