A simplified theory of crystallisation induced by polymer chain scissions for biodegradable polyesters
Open accessAbstract
A simplified theory for the crystallisation of biodegradable polyesters induced by polymer chain scissions during biodegradation is presented following a theory developed by Han and Pan. The original theory is greatly simplified so that it becomes very straightforward to use and the number of material parameters is significantly reduced. Furthermore it is demonstrated that the spherulite structure widely observed in polymers can be taken into account using the theory. The simplified theory is fitted to the experimental data of poly-l-lactic acids (PLLAs) obtained from literature. It is shown that the simplified theory is equally able to fit the data as the original one. It is also shown that the theory can fit degradation data for PLLAs of different initial degrees of crystallinity with spherulite structures.
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SEM voids may correspond to areas where significant auto-catalysis has occurred, resulting in pockets of low molecular weight oligomers that diffuse slowly out through the polymer matrix.
“This is consistent with SEM observations, where the voids seen may correspond to areas where significant auto-catalysis has occurred, resulting in pockets of low molecular weight oligomers which diffuse slowly out through the polymer matrix [21, 47].”
From Tuning structural relaxations, mechanical properties, and degradation timescale of PLLA during hydrolytic degradation by blending with PLCL-PEG (2019) · cites this paper as [21]
Section 3 links auto-catalytic degradation with hollow specimens, and section 4 suggests faster auto-catalytic degradation in some polymer regions. Section 2 says chain scission produces diffusible oligomers, but it does not identify SEM voids as oligomer-filled pockets or establish that the oligomers diffuse slowly through the matrix; the simplified model explicitly omits oligomer diffusion. Page numbers are unavailable in our copy. (LLM, conf=0.84)
Experimental — accuracy not yet measuredCrystallisation of PLLA occurs during degradation when hydration and hydrolysis-induced chain scission provide additional chain mobility.
“it also occurs during degradation when hydration and hydrolysis-induced chain scission provide additional chain mobility [20-22].”
From Tuning structural relaxations, mechanical properties, and degradation timescale of PLLA during hydrolytic degradation by blending with PLCL-PEG (2019) · cites this paper as [21]
Embrittlement of PLLA can be caused by either enthalpy relaxation or crystallisation.
“This embrittlement can be caused by either enthalpy relaxation or crystallisation.”
From Tuning structural relaxations, mechanical properties, and degradation timescale of PLLA during hydrolytic degradation by blending with PLCL-PEG (2019) · cites this paper as [21]
The Introduction says crystallinity affects PLLA’s mechanical properties, but it does not say crystallisation causes embrittlement. Searches for embrittlement and enthalpy relaxation found no passage addressing either proposed cause of embrittlement. (LLM, conf=0.72)
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References 23 · Cited by 67
Research works printed but not linked: 1
- Li SM, Garreau H, Vert M. Structureeproperty relationships in the case of the degradation of massive aliphatic poly-(a-hydroxy acids) in aqueous media. J Mater Sci Mater Med 1990;1:123e30.
- Authors
- Gleadall, A., Pan, J., & Atkinson, H.
- Affiliations
- University of Leicester (GB)
- Corresponding author
- Pan, Jingzhe
- Venue
- Polymer Degradation and Stability
- Publisher
- Elsevier BV
- Published
- 2012-09
- Volume
- 97
- Issue
- 9
- Pages
- 1616-1620
- ISSN
- 0141-3910 (ISSN-L)
- OpenAlex
- W2092734670
- Cited by
- 67
- References
- 23
- Citations by year
- 2026: 4 · 2025: 4 · 2024: 5 · 2023: 7 · 2022: 11 · 2021: 5 · 2020: 6 · 2019: 7 · 2018: 2 · 2017: 3 · 2016: 4 · 2015: 2 · 2014: 4 · 2013: 2
- FWCI
- 1.04
- Type
- journal article
- Language
- en
- Open access
- hybrid
- doi.org
- Licence
- Locations
- Polymer Degradation and Stability (publishedVersion, cc-by)
- Loughborough University Institutional Repository (Loughborough University) (submittedVersion, cc-by)
- Loughborough University Research Repository (Loughborough University) (submittedVersion, cc-by)
- Leicester Research Archive (University of Leicester) (submittedVersion)
- Funders
- Engineering and Physical Sciences Research Council
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Materials Chemistry › Thermal and Kinetic Analysis
- Keywords
- crystallization, polymer chain scission, biodegradable polyesters, poly(L-lactic acid), biodegradation, spherulitic structure, simplified theory, crystallinity, polymer degradation kinetics
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