Abstract Shear-induced formation of crystal nuclei in polyamide 11 (PA 11) was studied using a conventional parallel-plate rheometer. Crystallization of PA 11 after shearing the melt at different rates for 60 s was followed by the evolution of the complex viscosity. The sheared samples showed in an optical microscope a gradient structure along the radius, due to the increasing shear rate from the center to the edge. The critical shear rate for shear-induced formation of nuclei was identified at the position where a distinct change of the semicrystalline superstructure is observed, being at around 1 to 2 s −1 . Below this threshold, a space-filled spherulitic superstructure developed as in quiescent-melt crystallization. Above this value, after shearing at rates between 1 and 5 s −1 , an increased number of point-like nuclei was detected, connected with formation of randomly oriented crystals. Shearing the melt at even higher rates led to a further increase of the nuclei number and growth of crystals oriented such that the chain axis is in parallel to the direction of flow. In addition, optical microscopy confirmed formation of long fibrillar structures after shearing at such condition. The critical specific work of flow of PA 11 was calculated to allow a comparison with that of polyamide 66 (PA 66). This comparison showed that in the case of PA 11 more work for shear-induced formation of nuclei is needed than in the case of PA 66, discussed in terms of the chemical structure of the repeat unit in the chains. Graphical abstract
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Competition between Heterogeneous Nucleation and Flow‐Induced Crystallization of Polyamide 66 and Its Carbon Nanotube Composites
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−1in PA 66 neat resin to a rate faster than 4000 K s−1in 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.
more » « less- NSF-PAR ID:
- 10370666
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Macromolecular Rapid Communications
- Volume:
- 43
- Issue:
- 24
- ISSN:
- 1022-1336
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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