Mechanical activation of the transfer process in polymer systems

Mechanical activation (change in reactivity or activation energy) of polymer systems with a locally nonequilibrium (relaxation) response to mechanical perturbations is studied. Mechanical activation in such systems is caused by deviation of the medium microstructure from the state of local thermodynamic equilibrium. A system of equations for shear and uniaxial (elongation) deformation modes is formulated. The influence of local nonequilibrium in the medium microstructure on the mechanism and regular features of the macroscopic transfer process and also the effect of the stressed state of the polymer system and structural, kinetic, and orientation (steric) factors on the reactivity of polymer systems are analyzed. It is demonstrated that the reactivity of systems with a complicated internal structure has an energetic entropic character and depends on the reaction zone size (effect of a “nanoreactor”). The ranges of mechanical activation parameters affecting the reactivity and activation energy of polymer systems are determined for the shear and uniaxial modes of their deformation.