Zero growth temperature and growth kinetics of crystallizing poly(ε-caprolactone)

The lateral growth rate of polymer crystallites rises exponentially with decreasing temperature, thus indicating control by an activation step. Conventional wisdom assumes that the height of the activation barrier diverges at the equilibrium melting point together with the size of a secondary nucleu...

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Bibliographic Details
Published in:Colloid and polymer science 2007-05, Vol.285 (8), p.931-934
Main Authors: CHO, T.-Y, STILLE, W, STROBL, G
Format: Article
Language:English
Subjects:
Activation
Applied sciences
Barriers
Crystal growth
Crystallites
Crystallization
Exact sciences and technology
Growth rate
Melting points
Melts
Mesophase
Optical microscopes
Organic polymers
Physicochemistry of polymers
Properties and characterization
Spherulites
Temperature
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Summary:The lateral growth rate of polymer crystallites rises exponentially with decreasing temperature, thus indicating control by an activation step. Conventional wisdom assumes that the height of the activation barrier diverges at the equilibrium melting point together with the size of a secondary nucleus. Growth rate measurements for spherulites of poly(ϵ-caprolactone) carried out in a polarizing optical microscope at a series of stepwise increasing temperatures contradict this assumption. The barrier height is inversely proportional to the distance to the ‘zero growth temperature’ Tzg=77 °C , which is far below the equilibrium melting point =99 °C . The observation lends further support to our view that crystal growth is mediated by a transient mesophase. Tzg is to be identified with the temperature of the hidden transition between the melt and the mesophase.
ISSN:0303-402X
1435-1536
DOI:10.1007/s00396-007-1650-8