Self-nucleation and crystallization kinetics of double crystalline poly(p-dioxanone)-b-poly(ε-caprolactone) diblock copolymers
Open accessAbstract
The crystallization kinetics of each constituent of poly(p-dioxanone)-b-poly(epsilon-caprolactone) diblock copolymers (PPDX-b-PCL) has been determined in a wide composition range by differential scanning calorimetry and compared to that of the equivalent homopolymers. Spherulitic growth rates were also measured by polarized optical microscopy while atomic force microscopy was employed to reveal the morphology of one selected diblock copolymer. It was found that crystallization drives structure formation and both components form lamellae within mixed spherulitic superstructures. The overall isothermal crystallization kinetics of the PPDX block at high temperatures, where the PCL is molten, was determined by accelerating the kinetics through a previous self-nucleation procedure. The application of the Lauritzen and Hoffman theory to overall growth rate data yielded successful results for PPDX and the diblock copolymers. The theory was applied to isothermal overall crystallization of previously self-nucleated PPDX (where growth should be the dominant factor if self-nucleation was effective) and the energetic parameters obtained were perfectly matched with those obtained from spherulitic growth rate data of neat PPDX. A quantitative estimate of the increase in the energy barrier for crystallization of the PPDX block, caused by the covalently bonded molten PCL as compared to homo-PPDX, was thus determined. This energy increase can dramatically reduce the crystallization rate of the PPDX block as compared to homo-PPDX. In the case of the PCL block, both the crystallization kinetics and the self-nucleation results indicate that the PPDX is able to nucleate the PCL within the copolymers and heterogeneous nucleation is always present regardless of composition. Finally, preliminary results on hydrolytic degradation showed that the presence of relatively small amounts of PCL within PPDX-b-PCL copolymers substantially retards hydrolytic degradation of the material in comparison to homo-PPDX. This increased resistance to hydrolysis is a complex function of composition and its knowledge may allow future prediction of the lifetime of the material for biomedical applications.
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In weakly segregated systems (low χN values, T_ODT > Tc > Tg), there is little morphological restriction for crystallization, allowing a break out from the ordered melt structure, so crystallization determines the final structure, usually forming crystalline lamellae and erasing the previous melt structure.
“In this case, there is little morphological restriction for the crystallization process, which allows a break out from the ordered melt structure, therefore the crystallization determines the final structure, usually crystalline lamellae are formed, erasing the previous structure of the melt [ 102 , 103 , 109 , 121 , 125 , 150-153 , 160-171 ].”
From Fractionated crystallization in semicrystalline polymers (2021) · cites this paper as [121]
Similar results where a crystallizable block is affected by a second rubbery block during isothermal crystallization have been reported for PPDX-b-PCL diblock copolymers.
“Similar results where a crystallizable block is affected by a second rubbery block during isothermal crystallization has been reported by some of us for PPDXb -PCL diblock copolymers. [7,12]”
The understanding of the complicated properties of double crystalline diblock copolymer systems is still at a nascent stage.
“Although there have been a number of prior reports on double crystalline diblock copolymer systems, the understanding of their complicated properties is still at a nascent stage. [5-16]”
For PPDX-b-PCL, the spherulitic growth rate of the PPDX block was an order of magnitude lower than that of neat PPDX within block copolymers with only 23 wt % of molten PCL.
“It is noteworthythat for more strongly segregated systems (but still weakly segregated) as PPDXb -PCL, the spherulitic growth rate of the PPDX block was an order of magnitude lower than that of neat PPDX within block copolymers with only 23 wt % of molten PCL. 84”
From Crystallization Kinetics and Morphology of Biodegradable Double Crystalline PLLA- <i>b</i> -PCL Diblock Copolymers (2010) · cites this paper as [84]
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- Authors
- Müller, A. J., Albuerne, J., Marquez, L., Raquez, J.-M., Degée, P., Dubois, P., Hobbs, J., & Hamley, I. W.
- Affiliations
- Universidad Simón Bolívar (VE)
- University of Mons (BE)
- University of Sheffield (GB)
- University of Leeds (GB)
- Corresponding author
- Müller, Alejandro J.
- Venue
- Faraday Discuss.
- Publisher
- Royal Society of Chemistry (RSC)
- Published
- 2005
- Volume
- 128
- Pages
- 231-252
- ISSN
- 1359-6640 (ISSN-L)
- 1364-5498
- OpenAlex
- W2044835037
- Cited by
- 141
- References
- 58
- Citations by year
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- FWCI
- 9.25
- Type
- journal article
- Language
- en
- Open access
- green
- orbi.umons.ac.be
- Licence
- other-oa
- Locations
- Faraday Discussions (publishedVersion)
- PubMed (publishedVersion)
- ORBi UMONS (submittedVersion, other-oa)
- PolyPublie (École Polytechnique de Montréal) (submittedVersion)
- Funders
- Australian Government
- Fondo Nacional de Ciencia Tecnología e Innovación
- Services Fédéraux des Affaires Scientifiques, Techniques et Culturelles
- Office of Science
- 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 › Block Copolymer Self-Assembly
- Keywords
- diblock copolymers, self-nucleation, crystallization kinetics, spherulitic growth rate, Lauritzen-Hoffman theory, heterogeneous nucleation, lamellar morphology, isothermal crystallization, hydrolytic degradation, biodegradable polymers, block copolymer morphology
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