ABSTRACT
Both heterogeneous nucleation and flow-induced entropy reduction are the two well-known factors that accelerate polymer crystallization. However, the interplay of nucleation and flow-induced acceleration is still poorly understood. This work investigates the nucleating effect of carbon nanotubes (CNT) on both the quiescent and flow-induced crystallization kinetics of polyamide 66 (PA 66). The quiescent crystallization study indicates that CNT acts as a powerful nucleant, as suggested by the fact that the critical cooling rate to bypass crystallization and create the amorphous glassy state changes from 1000 K s-1 in PA 66 neat resin to a rate faster than 4000 K s-1 in the PA 66 nanocomposites. The flow-induced crystallization study indicates PA 66 onset crystallization time and morphology depend on the shear work introduced by rotational rheometry. A combined acceleration effect from CNT nucleants and flow-induced crystallization (FIC) persists when the CNT loading is under the saturation limit. However, if CNT loading meets the saturation limit, specific shear work shows no impact on the crystallization time, providing evidence that the role of the FIC acceleration effect no longer exists when nucleant acceleration dominates the crystallization of PA 66.
ABSTRACT
In a previous work on a poly(ether ether ketone) (PEEK) melt, above its nominal melting temperature (Tm â 335 °C), a severe Cox-Merz rule failure was observed. The abrupt decrease in the apparent shear viscosity was ascribed to the formation of flow-induced crystallization precursors. Here shear rheology and reflection polariscope experiments are utilized to unravel the structural changes occurring under shear on a similar PEEK melt above Tm. Three regimes of the flow curve were identified from low (0.01 s-1) to high shear rates (1000 s-1): (I) an isotropic structure with weak birefringence due to polymer chain orientation and mild shear thinning for Î³Ì < 1 s-1, (II) an isotropic-nematic transition accompanied by strong birefringence, two steady-state viscosities, and large nematic polydomain director fluctuations, and (III) shear-thinning behavior with an η ⼠γÌ-0.5 dependence for Î³Ì > 20 s-1, typically found in nematic fluids. The findings reported in this experimental work suggest that the nematic phase may represent the early stage of the formation of shear-induced crystallization precursors.
ABSTRACT
The role of an interval of shear flow in promoting the flow-induced crystallization (FIC) for poly(ether ether ketone) PEEK was investigated by melt rheology and calorimetry. At 350 °C, just above the melting temperature of PEEK (Tm), a critical shear rate to initiate the formation of flow-induced precursors was found to coincide with the shear rate at which the Cox-Merz rule abruptly begins to fail. In cooling the sheared samples to 320 °C, FIC can be up to 25× faster than quiescent crystallization. Using rheology and differential scanning calorimetry, the stability of FIC-induced nuclei was investigated by annealing for various times at different temperatures above Tm. The persistence of shear-induced structures slightly above Tm, along with complete and rapid erasure of FIC-induced nuclei above the equilibrium melting temperature, suggests that FIC leads to thicker lamellae compared with the quiescently crystallized samples.
