Rheooptical Fourier transform infrared spectroscopy of the deformation behavior in quenched and slow-cooled isotactic polypropylene films

摘要

Emerging technological applications for complex polymers require insight into the dynamics of these materials from a molecular and nanostructural viewpoint. To characterize the orientational response at these length scales, we developed a versatile rheooptical Fourier transform infrared (FTIR) spectrometer by combining rheometry, polarimetry, and FTIR spectroscopy. This instrument is capable of measuring linear infrared dichroism spectra during both small-strain dynamic deformation and large-strain irreversible deformation over a wide temperature range. The deformation response of quenched and slow-cooled isotactic polypropylene (iPP) is investigated. In quenched iPP, under dynamic oscillatory strain at an amplitude of similar to0.1%, the dichroism. from the orientation of the amorphous chains is appreciably less than that from the crystalline region. At large irreversible strains, we measured the dichroic response for 12 different peaks simultaneously and quantitatively. The dichroism from the crystalline peaks is strong as compared to amorphous peaks. In the quenched sample, the dichroism from the crystalline region saturates at 50% strain, followed by a significant increase in the amorphous region dichroism. This is consistent with the notion that the crystalline regions respond strongly before the yield point, whereas the majority of postyielding orientation occurs in the amorphous region. Our results also suggest that the 841 cm(-1) peak may be especially sensitive to the 'smectic' region orientation in the quenched sample. The response of the slow-cooled sample at 70 degreesC is qualitatively similar but characterized by a stronger crystalline region dichroism. and a weaker amorphous region dichroism, consistent with the higher crystallinity of this sample, and faster chain relaxation at 70 degreesC. (C) 2002 Wiley Periodicals, Inc. [References: 81]