Article (Scientific journals)
Self-nucleation and crystallization kinetics of double crystalline poly(p-dioxanone)-b-poly(e-caprolactone) diblock copolymers
Müller, Alejandro J; Albuerne, J.; Marquez, L. et al.
2005In Faraday Discussions, 128, p. 231-252
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Abstract :
[en] The crystallization kinetics of each constituent of poly(p-dioxanone)-b-poly(?-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.
Disciplines :
Chemistry
Author, co-author :
Müller, Alejandro J
Albuerne, J.
Marquez, L.
Raquez, Jean Marie  
Degée, Philippe
Dubois, Philippe  ;  Université de Mons > Faculté des Sciences > Matériaux Polymères et Composites
Hobbs, J.
Hamley, I.W.
Language :
English
Title :
Self-nucleation and crystallization kinetics of double crystalline poly(p-dioxanone)-b-poly(e-caprolactone) diblock copolymers
Publication date :
01 January 2005
Journal title :
Faraday Discussions
ISSN :
1359-6640
eISSN :
1364-5498
Publisher :
Royal Society of Chemistry, United Kingdom
Volume :
128
Pages :
231-252
Peer reviewed :
Peer Reviewed verified by ORBi
Research unit :
S816 - Matériaux Polymères et Composites
Research institute :
R400 - Institut de Recherche en Science et Ingénierie des Matériaux
Commentary :
Lecture en ligne: http://www.rsc.org/delivery/_ArticleLinking/DisplayArticleForFree.cfm?doi=b403085k&JournalCode=FD
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