Possible manifestations of the quantum effect (Tunneling) in elementary events in the fracture kinetics of polymers

Abstract

An elementary event in the kinetics of fracture of polymers, i.e., breaking of a stressed skeletal bond in a chain molecule, has been simulated by the decay of a loaded quantum anharmonic oscillator. The probability and the average time of expectation of the escape of a particle from the potential well in the Morse potential under the action of a tensile force have been calculated over a wide range of temperatures. It has been demonstrated that the escape of the particle occurs predominantly through the tunneling mechanism at low and medium temperatures and through a combination of the tunneling (under-barrier) and over-barrier (thermal-fluctuation) mechanisms with comparable contributions at high temperatures. The calculations have revealed that the participation of the tunneling mechanism in the kinetics of fracture of polymers manifests itself in a low-temperature athermal plateau in the temperature dependence of the breaking strength. A comparison between the calculated and experimental temperature dependences of the breaking strength for the oriented polymer polycaproamide has shown that the calculated and experimental results are in qualitative and quantitative agreement, which allows the conclusion that the tunneling mechanism can contribute to the fracture of polymers.