Edmund Arthur Flexman

Effect of miscible polymer diluents on the development of lamellar morphology in poly(oxymethylene) blends

The development of lamellar morphology in poly(oxymethylene) (POM) and its miscible blends was studied by synchrotron time-resolved small-angle X-ray scattering (SAXS), during primary and secondary crystallization at temperatures near 150°C. The blends contained two different diluents: poly(vinyl 4-hydroxy styrene) [common name poly(vinyl phenol), (PVP)], which had a high glass temperature (Tg = 150°C), and styrene-co-hydroxy styrene oligomer (PhSO), which had a low glass temperature (Tg = −37°C). The SAXS data were analyzed by correlation function analysis to extract several lamellar parameters: long period (L), lamellar crystalline thickness (lc), amorphous layer thickness (la), and invariant (Q). The variation in Q defined the region where spherulites quickly grew and filled the entire space, and was referred to as the primary crystallization dominant regime. A rapid drop in L and lc was observed at early times, and this can be explained by defective lamellar stacks filling in space between primary stacks, as secondary crystals form during the nominal primary crystallization dominant regime. Lamellar thickening with time in the long-time secondary crystallization region was observed in neat POM and the blend with 10 % low Tg diluent, while this process was inhibited with the high Tg diluent due to the higher Tg of the interlamellar species. A decrease in la at long times confirmed the lamellar thickening. We refer to the lamellar thickening process as a type of secondary crystallization. Interlamellar inclusion or trapping was detected to different degrees with the high Tg diluent, while exclusion was found for the low Tg diluent.

A.C. dielectric and TSC studies of constrained amorphous motions in flexible polymers including poly(oxymethylene) and miscible blends

Poly(oxymethylene) ( POM ) and its miscible blends were studied by multifrequency A.C. dielectric and thermally stimulated currents (TSC). The blends contained small amounts of either poly(vinyl phenol), which is a high glass transition (T g diluent, or a styrene-co-hydroxy styrene oligomeric low T g diluent. The variation of the 10°C β transition with blend composition proves that it is the glass transition, and that the -70°C y transition is a local motion. Dielectrically the P transition is very weak in pure POM even in fast-quenched samples. The TSC thermal sampling method also detected two cooperative transitions, and β, in POM and its blends, and was used to directly resolve the transition into low and high activation energy components. If one considers the contribution of exclusion of the diluents from the crystal lamellae, it is shown that the blends behave like typical amorphous blends as a function of concentration. The effect of crystals on amorphous motions is examined in light of comparison with van Krevelens 37 predictions of an amorphous T g , and the transitions in POM are contrasted with those for other semicrystalline polymers.

Dynamic mechanical characterization of relaxations in poly(oxymethylene), miscible blends, and oriented filaments

Abstract Multifrequency dynamic mechanical analysis (DMA) data were obtained for molded poly(oxymethylene) (POM) and its blends from-150°C to 150°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 β transition in the POM blends favors an assignment of the β transition detected at −3°C(1 Hz), not the −80°C γ transition, as the T g in semicrystalline POM because the latter is invariant with diluent. The peak at the β transition in pure POM is weak and can only be seen clearly by DMA measurements on samples that have not “aged” at ambient temperature. This is further evidence that the β transition arises from a cooperative glass-transition-like motion. The γ transition is not influenced by aging because it is due to a concerted localized main chain motion. The β transition of an orien...

DYNAMICS IN POLY(OXYMETHYLENE) AND POLY(OXYMETHYLENE-CO-OXYETHYLENE) AS STUDIED VIA A COMBINED CREEP RATE SPECTROSCOPY/DIFFERENTIAL SCANNING CALORIMETRY APPROACH

The peculiarities and kinetics of segmental dynamics in a few semi-crystalline poly(oxymethylene) (POM) samples and in poly(oxymethylene-co-oxyethylene) with 1.5% ethylene oxide units were studied over the temperature range from 110 to 430K. Differential scanning calorimetry (DSC) and laser-interferometric creep rate spectroscopy (CRS) were used. The latter was operated under uniaxial tension or compression. A number of dynamic anomalies were observed. These included a suppressed glass transition (T g) with its transformation into segmental relaxations below and above T g, and a pronounced dynamic heterogeneity, with the dispersion of activation energies of segmental motion ranging from 60 to 500 kJ mol−1. Formation of anomalous long folds in POM and the copolymer structure is assumed from DSC data, indicating a predominant contribution of “straightened out” tie chains to the structure of disordered regions in these isotropic polymers. Discrete high-resolution CRS analysis showed that numerous peaks (separate types of segmental motion) constituted dynamics in the interlamellar layers of the polymers under study. Considerable influence of comonomer or small additives, or preliminary treatments (quenching, small pre-straining) on discrete CR spectra was observed and are discussed in the text. All the anomalies observed could be treated in terms of the concept of the common segmental nature of α and β relaxations in flexible-chain polymers; as the breakdown of intermolecular motional cooperativity due to nanoscale confinement effect, and as a different constraining influence of crystallites on dynamics in the intercrystalline layers.