Macromolecular chain scission under mechanical stress has been studied by infrared spectroscopy. The dependence of accumulation of chemical bond scissions on temperature T and uniaxial tensile stress σ has been investigated. The rate constant K for bond dissociation under mechanical stress has been found to obey the modified Arrhenius equation: K = K0 exp{ − (EA − ασ)/RA}. The quantitative connection between the rate constant for bond dissociation and mechanical lifetime τ has been established. Analysis of the experimental data indicates that the strength and mechanical lifetime of polymers is determined by the kinetics of mechanochemical scission of the main chains of polymer molecules.

SynopsisSubmicrocracks, free radicals, and endgroups of scissioned molecules formed in polyethylene, polypropylene, and polycaprolactam under uniaxial tension have been investigated. Measurements were carried out by small-angle x-ray scattering, electron paramagnetic resonance, and infrared spectroscopy. The concentration of submicrocracks is almost the same as that of free radicals but is smaller than the concentration of scissioned macromolecules by approximately three orders of magnitude. The number of scissions per crack proved to be close to the number of macromolecules passing through the cross section of a submicrocrack calculated on the assumption of close packing. It is concluded that submicrocracks in stressed polymers are formed as a result of chain reactions of macromolecular decomposition initiated by the active end primary free radicals. 1509

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There are two distinctive channels in the dissociation reaction of O2 on Si(001)-(2 x 1): a trapping-mediated channel and a direct-activated channel. Externally applied tensile strain along the <110> direction on the (001) surface is found to suppress the dissociation via a direct-activated channel and to enhance that via a trapping-mediated channel in the temperature range between 200 and 300 K. It has been demonstrated that the dissociation dynamics involving elementary processes such as inelastic scattering and trapping, desorption and/or dissociation from a trapping precursor, and direct dissociation are sensitively influenced by the strain to change the branching ratio of the dissociation reaction.