My. Keating et al., DYNAMIC-MECHANICAL CHARACTERIZATION OF RELAXATIONS IN POLY(OXYMETHYLENE), MISCIBLE BLENDS, AND ORIENTED FILAMENTS, Journal of macromolecular science. Physics, 36(6), 1997, pp. 717-732
Multifrequency dynamic mechanical analysis (DMA) data were obtained fo
r molded poly(oxymethylene) (POM) and its blends from -150 degrees C t
o 150 degrees C. Because of the high crystallinity, the assignment of
the glass transition in POM has been controversial in the literature.
Low and high glass transition temperature (T-g) phenolated compounds,
including poly(vinyl phenol), were found to be miscible with POM. The
shift of the beta transition in the POM blends favors an assignment of
the beta transition detected at -3 degrees C (1 Hz), not the -80 degr
ees C gamma transition, as the T-g in semicrystalline POM because the
latter is invariant with diluent. The peak at the beta transition in p
ure POM is weak and can only be seen clearly by DMA measurements on sa
mples that have not ''aged'' at ambient temperature. This is further e
vidence that the beta transition arises from a cooperative glass-trans
ition-like motion. The gamma transition is not influenced by aging bec
ause it is due to a concerted localized main chain motion. The beta tr
ansition of an oriented POM filament can be seen in the DMA flexural l
oss spectrum at -18 degrees C (1 Hz), but not in a tensile loss spectr
um. The broad a relaxation was detected at about 110 degrees C (1 Hz)
in molded POM and its blends, while it was shifted to about 135 degree
s C in the higher crystallinity, oriented system. The alpha peak is al
so independent of diluent, consistent with a crystalline origin for th
is transition, as was proposed earlier.