Crystallization studies of poly(ε‐caprolactone).I. Morphology and kinetics

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Abstract
The crystallization behavior of three molecular weight samples of poly(ε‐caprolactone) has been studied as a function of temperature. Crystallization begins in the form of axialities and changes to spherulite growth as time progresses, presumably owing to the molecular weight distribution. Determinations of equilibrium melting point and analyses of growth kinetics are complicated by a major lamellar thickening process occurring at the crystallization temperature. Secondary nucleation analyses of spherulitic growth rates, carried out assuming a similar growth face to that of polyethylene, result in values of σσe. Use of the Thomas–Stavely relation to calculate a value of σ results in values of fold‐surface free energy, σe, similar to that of polyethylene.