By K. Bode, I. Kuriyama, J.E. Mark, F. Maser, M. Mutter, Y. Nakose, A. Odajima, V.N.R. Pillai, J.P. Queslel, H.W. Siesler
With contributions via various specialists
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As expected from the stress-strain diagram no crystallization can be detected in the radiation-crosslinked synthetic 1,4-cis-polyisoprene (Fig. 37c). The relative shift of the structural absorbance ratios to higher values is merely due to a different baseline evaluation of the reference band for this polymer. An interesting effect becomes evident when the structural absorbance of the v(C-- C) thickness reference band is plotted as a function of strain (Fig. 38) for the loadingunloading cycle of the strongly crystallizing system (Fig.
Apart from a general intensity decrease as a consequence of the reduction in sample thickness the intensities of the 1459/1455 cm -1 bands (not resolved here) of the crystalline at-modification drastically decrease while the intensity of the 1475/1470 cm -1 band complex exhibits a relative increase. This result can be attributed to the predominant formation of a fibrillar structure with the abovementioned imperfect all-trans conformation of the aliphatic segments. Once the neck has completely moved across the specimen (at about 350 ~ strain) stress increases linearly with strain.
Once the neck has completely moved across the specimen (at about 350 ~ strain) stress increases linearly with strain. To study the reversibility of the deformation the sample has been subjected to an unloading-loading cycle. The spectra taken during this cycle have been labeled 18-23 and the small intensity changes of the 1459/1455 cm -1 bands relative to the 1475/1470 cm -1 bands and the v(C--C) aromatic ring reference band at 1505 cm- ~ clearly reflect that there is only an extremely small portion of polymer chains reversibly recovering to the crumpled conformation upon unloading.