Crystal Modifications and Thermal Behavior of Poly( l -lactic acid) Revealed by Infrared Spectroscopy
Abstract
Recently, we reported the isothermal crystallization behaviors of poly( l -lactic acid) (PLLA) from the melt and glassy states, respectively [ J. Phys. Chem. B 2004, 108, 11514; Macromolecules 2004, 37, 6433]. Surprisingly, the quite different infrared (IR) spectral evolutions occur in the two crystallization processes at different temperatures in which the same crystal modification is expected to be formed. To clarify this unusual phenomenon, the crystal modifications and thermal behavior of PLLA samples prepared under different crystallization temperatures are investigated in detail by TEM, WAXD, and FTIR techniques. On the basis of the WAXD and IR data, a new crystal modification named the α form is proposed for the crystal structure of PLLA samples annealed at temperature below 120 °C. Such crystal modification with loose 10 3 helical chain packing is less thermally stable than the standard α form of PLLA. This assignment can explain all the experiment observations well. Other possible mechanisms for the IR spectral difference of bulk PLLA samples annealed at different temperatures are also discussed.
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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 [53]
For samples crystallized at high temperatures, no such exotherm could be observed.
“For the samples crystallized at high temperatures, no such exotherm could be observed. 51,53,59”
From Crystallization Kinetics and Morphology of Biodegradable Double Crystalline PLLA- <i>b</i> -PCL Diblock Copolymers (2010) · cites this paper as [53]
Zhang et al. showed by real-time FTIR that a more stable α' form is produced just below the melting point of PLLA when samples are isothermally crystallized at temperatures below 120 °C.
“Zhang et al. 53 showed by real-time FTIR that a more stable R form, referred to as the R 0 form (the R form is believed to arise from cold-crystallization or crystallization from the melt), is produced just below the melting point of the PLLA sample when the samples were isothermally crystallized at temperatures below 120 ° C.”
From Crystallization Kinetics and Morphology of Biodegradable Double Crystalline PLLA- <i>b</i> -PCL Diblock Copolymers (2010) · cites this paper as [53]
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- Authors
- Zhang, J., Duan, Y., Sato, H., Tsuji, H., Noda, I., Yan, S., & Ozaki, Y.
- Affiliations
- Toyohashi University of Technology (JP)
- Corresponding author
- Ozaki, Yukihiro
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2005-08-20
- Volume
- 38
- Issue
- 19
- Pages
- 8012-8021
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2033791433
- Cited by
- 893
- References
- 3
- Citations by year
- 2026: 32 · 2025: 34 · 2024: 43 · 2023: 55 · 2022: 60 · 2021: 39 · 2020: 52 · 2019: 77 · 2018: 53 · 2017: 65 · 2016: 66 · 2015: 55 · 2014: 46 · 2013: 46 · 2012: 45
- FWCI
- 11.16
- 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 › Material Dynamics and Properties
- Keywords
- poly(L-lactic acid), crystal modifications, α-form, isothermal crystallization, thermal stability, annealing temperature, polymer crystallization
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