Morphological heterogeneity of polymer fibers which do not reveal small‐angle x‐ray reflections

Abstract

SynopsisFor many aliphatic and wholly aromatic polymer fibers, meridional small-angle x-ray reflections (SAXR's) are not observed. The morphological features which give rise to this effect have received little attention in the literature. I t is sometimes speculated that this is evidence of a morphological homogeneity along the fiber axis (no fluctuation of electron density-no long periods), ignoring other possible reasons (morphology is heterogeneous but very irregular or the maximum intensity of SAXR ( I -) is low and SAXR cannot be observed against the background of diffuse scattering.) Fibers with homogeneous crystalline morphology should have an elastic modulus E, clase to that of the crystallites E,, along the polymer chains over a broad range of stresses. Rut, as was found in this work for the overwhelming majority of such nonreflection fibers (including Kevlar aramid fibers) there is a considerable difference between E,, and E, (for some nonreflection fibers the ratio E,/E, is on the order of 10). This means that their morphology is heterogeneous along the fiber axis and contains "weaker" intercrystalline regions. This heterogeneity appeared to be regular enough to give rise to SAXR, as determined from the appearance of SAXR during elastic extension and after the beginning of pyrolysis in some nonreflection fibers. Thus, it was concluded that the lack of observable SAXR for these fibers is a result of the weakness of I,,relative to the diffuse scattering. Support for this statement is seen in the analysis of the decrease of I,,,, to zero with increasing draw ratio for poly(viny1 alcohol) fibers.The key factors influencing the decrease of I,, in this case were found to be the decrease of fibril diameter (fibril splitting), an increase of the dispersion of the long periods and some possible decrease in the density difference between crystalline and amorphous regions. The particular combinations of such factors can be different for each particular case of missing SAXR and are discussed in this paper.

Analysis of structure and properties of poly(ethylene terephthalate) fibers

“…It has also been reported that in some cases, because of the strong diffuse scattering, a long period cannot be observed for fibers that still possess a regular heterogeneity along the fiber axis. 51 During annealing some of the intermediate phase which connects to the crystals can crystallize, and the intermediate phase chains which connect to the amorphous phase may relax and lose some of their orientation. Both an increase in crystallinity and shrinkage have been observed on annealing.…”

SAXS investigations of isotactic polypropylene (IPP) fibres mass coloured with organic pigments

“…When fibres are drawn, the intercrystalline amorphous regions in the fibrillar structure are displaced and the mean thickness of the amorphous region is increased resulting in the increase of the long period. Since each amorphous region contains a different number of macromolecules it is shifted to a different distance and, according to Slutsker (1987), a broadening and reduction of the reflection is observed. At higher drawing, the dispersion of long period is increased and this results in reduction of the reflection to such an extent that it is no longer observed.…”