Polymorphous Crystallization and Multiple Melting Behavior of Poly( l -lactide): Molecular Weight Dependence
Abstract
The effect of molecular weight (MW) on the polymorphous crystallization and melting behavior of poly( l -lactide) (PLLA) were systemically studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), wide-angle X-ray diffraction (WAXD), and time-resolved Fourier transform infrared (FTIR) spectroscopy. It was found that the polymorphism of PLLA is not influenced much by MW, and the α‘- and α-form crystals are produced at low and high crystallization temperature ( T c ), respectively, regardless of the MW. However, MW significantly affects the crystallization kinetics, and the crystallization rate reduces greatly with MW increasing. Moreover, the T c - and MW-dependent melting behavior of PLLA was clarified with combining the DSC and FTIR results. It was found that the α‘- to α-crystalline phase transition occurs prior to the dominant melting in both the low- and high-MW PLLA crystallized at low T c . Unlike the high-MW PLLA, in low-MW PLLA crystallized at low T c, the α‘-form crystals only partially transform into the α-one, and some amounts of α‘-form crystals melt directly without transition during the heating process. With increasing T c, the melting of PLLA with various MWs changes from the phase transition + melting mechanism to the usual melt−recrystallization mechanism.
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The high-temperature exothermic peak observed before the main melting peak in PLLA has been attributed to recrystallization or to the formation of a more stable crystalline phase.
“The one at high temperatures has been previously observed for PLLA homopolymers of different molecular weights during heating scans and has been attributed to recrystallization 49 -51 or to the formation of a more stable crystalline phase; see below. 14,52 -57”
From Crystallization Kinetics and Morphology of Biodegradable Double Crystalline PLLA- <i>b</i> -PCL Diblock Copolymers (2010) · cites this paper as [55]
The melting peak shoulder for PLLA 24 has been explained as a consequence of recrystallization and/or formation of a more stable crystalline phase.
“Similarly, the melting peak shoulder for PLLA 24 has been explained as a consequence of one or both phenomena. 49,51,55,58”
From Crystallization Kinetics and Morphology of Biodegradable Double Crystalline PLLA- <i>b</i> -PCL Diblock Copolymers (2010) · cites this paper as [55]
Tm values of polymers can be strongly affected by molecular weight below a critical value.
“T m values can be strongly affected by molecular weight below a critical value.”
From Crystallization Kinetics and Morphology of Biodegradable Double Crystalline PLLA- <i>b</i> -PCL Diblock Copolymers (2010) · cites this paper as [55]
The critical molecular weight below which Tm is strongly affected is apparently located at 30-40 kg/mol.
“If we consider T m values reported in the literature, 55,58,60,61 then this critical value is apparently located at 30 -40kg/mol”
From Crystallization Kinetics and Morphology of Biodegradable Double Crystalline PLLA- <i>b</i> -PCL Diblock Copolymers (2010) · cites this paper as [55]
The crystallization kinetics of PLLA is very much dependent on molecular weight; with increasing MW, the crystallization rate drops greatly.
“The crystallization kinetics of PLLA has been reported to be very much dependent on the molecular weight (MW). With increasing MW, the crystallization rate drops greatly. 55”
From Crystallization Kinetics and Morphology of Biodegradable Double Crystalline PLLA- <i>b</i> -PCL Diblock Copolymers (2010) · cites this paper as [55]
The spherulitic growth rate of PLLA crystals formed at identical temperatures decreased as the molecular weight increased.
“The spherulitic growth rate of PLLA crystals formed at identical temperatures decreased as the molecular weight increased.”
From Crystallization Kinetics and Morphology of Biodegradable Double Crystalline PLLA- <i>b</i> -PCL Diblock Copolymers (2010) · cites this paper as [55]
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- Authors
- Pan, P., Kai, W., Zhu, B., Dong, T., & Inoue, Y.
- Affiliations
- Tokyo Institute of Technology (JP)
- Corresponding author
- Inoue, Yoshio
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2007-08-18
- Volume
- 40
- Issue
- 19
- Pages
- 6898-6905
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W1976525237
- Cited by
- 679
- References
- 4
- Citations by year
- 2026: 27 · 2025: 25 · 2024: 39 · 2023: 35 · 2022: 45 · 2021: 30 · 2020: 37 · 2019: 54 · 2018: 47 · 2017: 55 · 2016: 47 · 2015: 50 · 2014: 34 · 2013: 35 · 2012: 29
- FWCI
- 17.08
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Materials Science › Materials Chemistry › Crystallization and Solubility Studies
- Keywords
- poly(L-lactic acid), polymorphism, crystallization kinetics, melting behavior, molecular weight dependence, alpha crystal, phase transitions, melt recrystallization, crystallization temperature, biodegradable polymers
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