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Polymers 2018, 10(2), 120; https://doi.org/10.3390/polym10020120

Nucleation Enhancement in Stereodefective Poly(l-lactide) by Free Volume Expansion Resulting from Low-Temperature Pressure CO2 Preconditioning

1
School of Biomedical Engineering, Southern Medical University, Guangzhou 510515, China
2
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, China
*
Authors to whom correspondence should be addressed.
Received: 25 December 2017 / Revised: 15 January 2018 / Accepted: 24 January 2018 / Published: 26 January 2018
(This article belongs to the Special Issue Phase Behavior in Polymers)
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Abstract

Nucleation enhancement in a highly stereodefective poly(l-lactide) (PLLA) with an optical purity of 88% by low-temperature pressure (0 and 35 °C under 2 MPa) CO2 preconditioning was investigated using differential scanning calorimetry (DSC), infrared (IR) spectroscopy, polarized optical microscopy (POM) as well as positron annihilation lifetime spectroscopy (PALS). Despite the preconditioning of the melt-quenched films for 2 h, IR results indicated that no trace of mesophase was generated and the samples remained in the glassy state. However, judging from the results of DSC, IR, and POM, when compared to the untreated sample, both the treated ones showed a significantly enhanced crystal nucleation effect, resulting in the corresponding greatly enhanced crystallization kinetics. Moreover, owing to the existence of the retrograde vitrification, the conditions of the previous low-pressure CO2 conditioning affected the nucleation enhancement effect. When compared to the case of 35 °C, the much lower temperature of 0 °C was more effective for nucleation enhancement. The PALS results indicated that the enlarged free volume, which resulted from the CO2 conditioning, largely accounted for the formation of locally ordered structures, providing many more potential nucleation sites for forming critical nuclei and thus the resulting enhanced crystallization kinetics in glassy PLLA. The present results have implications in understanding the nucleation enhancement effect, in particular in stereodefective PLLA systems, which possess extremely low crystallization ability and are thus probably too problematic to be evaluated by conventional methods. View Full-Text
Keywords: poly(l-lactide); carbon dioxide; nucleation; crystallization; free volume poly(l-lactide); carbon dioxide; nucleation; crystallization; free volume
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).
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Lan, Q.; Yu, J.; Zhang, J.; He, J. Nucleation Enhancement in Stereodefective Poly(l-lactide) by Free Volume Expansion Resulting from Low-Temperature Pressure CO2 Preconditioning. Polymers 2018, 10, 120.

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