Mechanisms of frequency shifting in the infrared spectrum of stressed polymer

In the vibrational spectrum of a polymer obtained under tensile stress loading conditions, several modes of molecular deformation can lead to different mechanisms of frequency shifting and asymmetric band deformation. Theoretically and experimentally it has been observed that quasielastic deformations (reduction of force constants due to bond weakening under stress), pure elastic bond stretching and angle bending, conformational variations, and several types of chain defects can cause linear shifts in frequency and infrared band distortion. A detailed study of the deformation spectra of isotactic polypropylene and polyphenyl‐ p ‐sulfide indicated that quasielastic and elastic mechanisms are the major contributors to frequency shifting, principally affecting stretching and bending vibrational modes. Conformational mechanisms can affect torsional modes whereas the defect mechanism, when present, can cause random distortion of an infrared band. The latter mechanism is difficult to quantize. The extent to which each mechanism contributes to the total spectral deformation can be a function of morphology, macroscopic loading conditions, thermal and strain histories.