Influence of Semicrystalline Morphology on the Glass Transition of Poly(L‐lactic acid)
Abstract
Summary: Semicrystalline specimens of poly(L‐lactic acid) (PLLA) were prepared by isothermal cold‐ or melt‐crystallization over a wide temperature range. The morphologies at different length scales were characterized using polarized optical microscopy, WAXS and SAXS. The glass transition temperature (Tg), determined calorimetrically, exhibited a general decrease with an increase in crystallization temperature (Tc) for either cold‐ or melt‐crystallized specimens. The measurements of the heat capacity increment at Tg indicated that a significant amount of the rigid amorphous fraction coexisted with the crystalline and mobile amorphous phases in semicrystalline PLLA. A three‐phase model (crystalline phase, mobile amorphous phase and rigid amorphous phase) is, therefore, appropriate for the interpretation of the structure of semicrystalline PLLA. According to a one‐dimensional layer stack model, the layer thicknesses of the three phases were further evaluated approximately. The increasing of Tg was found to be correlated to significant decreasing thickness of the crystalline layer, gradual decreasing thickness of the rigid amorphous layer, and a slight increasing trend in the thickness of the mobile amorphous layer. We suggest that the rigid amorphous layer of semicrystalline PLLA may possibly play a role in loosening the constraints imposed by the crystalline layer on the amorphous chain motions inherent to the glass transition. The optical microscopy photograph shows the spheru…
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No clear banded spherulites were observed for the PLLA homopolymer and PLLA block within the diblock copolymers.
“Noclear banded spherulites were observed in this work for the PLLAhomopolymerandPLLAblockwithinthediblockcopolymers, as reported in the literature for PLLA homopolymers. 80,82”
From Crystallization Kinetics and Morphology of Biodegradable Double Crystalline PLLA- <i>b</i> -PCL Diblock Copolymers (2010) · cites this paper as [80]
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BackgroundHsu, S.-T. (2013) · doi:10.7916/d8dz0ghx · Cited by 2 · see citing works
“The fraction of RAP in crystalline PLLA can be as large as around 20-30% (Wang et al., 2006; Sarasua et al., 2008), which inhibits the”
BackgroundPracaxi oil (Pentaclethra macroloba)-loaded nanofibers: a promising biomaterial for wound healing
Ricci-Júnior, E., Monteiro, L., de Lima, A. D., Toledo, A. L. M. M., Dias, M., Pádua, T. A., Costa, T., Machado, F. P., Ferreira, M., Rocha, L., et al. (2026) · Future Journal of Pharmaceutical Sciences · doi:10.1186/s43094-026-00938-3 · Cited by 1 · see citing works
Zhang, Y., Li, H.-F., An, L., & Jiang, S.-C. (2013) · doi:10.3724/sp.j.1105.2013.12362 · Cited by 1
Enhancing the Interface of PLA Composites Through Solution‐Based Processing
McKay, I., Yang, L., & Felfel, R. (2026) · Polymer Composites · doi:10.1002/pc.71772
Effect of Annealing on the Mechanical Properties of Carbon Fiber-Reinforced PLA
Perez-Solis, D., Martínez-Trinidad, J., Frutos, A., Coca-Gonzalez, M., & Jiménez-Martínez, M. (2026) · Polymers · doi:10.3390/polym18212721
Effect of self-nucleation on crystallization of as-received poly (lactic acid)
Yao, L. F., Ying, J., Yang, L., Geng, Q., Ding, H., & Wang, Y. (2025) · Journal of Thermal Analysis and Calorimetry · doi:10.1007/s10973-025-15108-5
“It has been reported that the size of spherulites in melt-crystallized PLA is much larger than that in cold-crystallized one [24, 25].”
Self-citationControl of Crystallization of Poly (Lactic Acid) Membranes
Sato, S., Shindo, R., Kanehashi, S., Nagai, K., & Hilal, N. (2015) · doi:10.1201/b18149-5
- Authors
- Wang, Y., Funari, S. S., & Mano, J. F.
- Affiliations
- 3B's Research Group (PT)
- Deutsches Elektronen-Synchrotron DESY (DE)
- Corresponding author
- Mano, João F.
- Venue
- Macromolecular Chemistry and Physics
- Publisher
- Wiley
- Published
- 2006-07-17
- Volume
- 207
- Issue
- 14
- Pages
- 1262-1271
- ISSN
- 1022-1352 (ISSN-L)
- 1521-3935
- OpenAlex
- W1965020155
- Cited by
- 104
- References
- 0
- Citations by year
- 2026: 1 · 2025: 3 · 2024: 4 · 2022: 5 · 2021: 5 · 2020: 6 · 2019: 10 · 2018: 6 · 2017: 11 · 2016: 4 · 2015: 2 · 2014: 4 · 2013: 7 · 2012: 2
- FWCI
- 6.55
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecular Chemistry and Physics (publishedVersion)
- DESY Publication Database (PUBDB) (Deutsches Elektronen-Synchrotron) (submittedVersion)
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Materials Chemistry › Material Dynamics and Properties
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Keywords
- poly(L-lactic acid), semicrystalline morphology, glass transition temperature, cold crystallization, melt crystallization, crystallization temperature, rigid amorphous phase, three-phase model, spherulitic morphology
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