Intracrystalline Dynamics in Oligomer‐Diluted Poly(Ethylene Oxide)

Abstract

Solid-state creep, ductility, and drawability are relevant mechanical properties of "crystal-mobile" polymers, related to a large-scale chain transport through the crystal, which is in turn mediated by intracrystalline monomer jumps. Here, high-M w poly(ethylene oxide) is used as a well-controlled model system, modulating the properties of the amorphous phase by diluting with a non-crystallized oligomer. Faster intracrystalline motions are found upon oligomer addition, indicating little changes in the fold surface and a dominant influence of the somewhat reduced lamellar thickness.

Recent Progress in Understanding Polymer Crystallization

“…[ 27 ] The dilution of high‐MW PEO with oligomers that preferentially remain in the amorphous phase was also found to enhance intracrystalline dynamics, on the one hand due to faster dynamics in the amorphous phase (enhancing the defect generation) and on the other hand due to somewhat thinner lamellae. [ 28 ]…”

“…[27] The dilution of high-MW PEO with oligomers that preferentially remain in the amorphous phase was also found to enhance intracrystalline dynamics, on the one hand due to faster dynamics in the amorphous phase (enhancing the defect generation) and on the other hand due to somewhat thinner lamellae. [28] Turning to mechanistic implications, in the late 1980's and still rooted in the influential HL model of secondary nucleation, [6] Hikosaka stressed the relevance of "chain-sliding diffusion" [29] within the (secondary) nucleus at the growth front. Together with Keller and coworkers, [30] a relation was established to the large lamellar thicknesses observed in poly(ethylene) crystallized under high pressure, which occurs through the highly mobile hexagonal rotator phase following Ostwald's rule of stages.…”

The Year of Polymers – 100 Years of Macromolecular Chemistry

“…The Saalwächter group examined the intracrystalline dynamics thereby elucidated that dilution with oligomers leads to faster intracrystalline motions. [6] In addition to the above-mentioned contributions, this special issue contains many more exciting articles in various fields of macromolecular science. In addition, a wide range of articles can be found in the other part of the double special in Macromolecular Rapid Communications.…”

“…Finally, another contribution is devoted to the study of one of today's most important polymers; poly(ethylene glycol). The Saalwächter group examined the intracrystalline dynamics thereby elucidated that dilution with oligomers leads to faster intracrystalline motions …”