Spherulitic Crystallization Behavior of Poly(ε-caprolactone) with a Wide Range of Molecular Weight
Poly(ε-caprolactone) (PCL) with a wide range of molecular weight (MW) has been prepared via fractionation by either precipitating PCL/chloroform solutions into different amounts of methanol or adding methanol into PCL/tetrahydrofuran (THF) solutions. The samples with M n ranging from 1900 to 64 700...
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Published in | Macromolecules Vol. 30; no. 6; pp. 1718 - 1722 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
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American Chemical Society
24.03.1997
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Abstract | Poly(ε-caprolactone) (PCL) with a wide range of molecular weight (MW) has been prepared via fractionation by either precipitating PCL/chloroform solutions into different amounts of methanol or adding methanol into PCL/tetrahydrofuran (THF) solutions. The samples with M n ranging from 1900 to 64 700 were used to investigate the MW effects on the spherulite growth rate, nucleation density, and equilibrium melting point (T m 0) of PCL. The variation of spherulite growth rate with MW exhibited a maximum rather than a conventional monotonic drop. The existence of such a maximum was rationalized by considering the interplay between the effects of MW on T m 0 and segmental mobility. A growth kinetic formula proposed by Hoffman was employed to extract the crystal surface free energy product (σσe). In contrast to the conventional Lauritzen−Hoffman analysis which was based on the growth rates measured at different crystallization temperatures (T c) for a given MW, the present analysis was based on the growth rates measured for different MW at a given T c. The spherulite nucleation density was found to be higher for the sample with larger MW, and this observation was interpreted based on the individual effects of MW on the primary nucleation rate and spherulite growth rate. An increase in MW promoted the nucleation rate much more significantly compared with its effect on the growth rate, and this in turn led to a higher nucleation density. An unusual morphology due to the segregation of uncrystallizable short chains into the interfibrillar regions of the spherulites was also observed for PCL with M n = 1900. |
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AbstractList | Poly(ε-caprolactone) (PCL) with a wide range of molecular weight (MW) has been prepared via fractionation by either precipitating PCL/chloroform solutions into different amounts of methanol or adding methanol into PCL/tetrahydrofuran (THF) solutions. The samples with M n ranging from 1900 to 64 700 were used to investigate the MW effects on the spherulite growth rate, nucleation density, and equilibrium melting point (T m 0) of PCL. The variation of spherulite growth rate with MW exhibited a maximum rather than a conventional monotonic drop. The existence of such a maximum was rationalized by considering the interplay between the effects of MW on T m 0 and segmental mobility. A growth kinetic formula proposed by Hoffman was employed to extract the crystal surface free energy product (σσe). In contrast to the conventional Lauritzen−Hoffman analysis which was based on the growth rates measured at different crystallization temperatures (T c) for a given MW, the present analysis was based on the growth rates measured for different MW at a given T c. The spherulite nucleation density was found to be higher for the sample with larger MW, and this observation was interpreted based on the individual effects of MW on the primary nucleation rate and spherulite growth rate. An increase in MW promoted the nucleation rate much more significantly compared with its effect on the growth rate, and this in turn led to a higher nucleation density. An unusual morphology due to the segregation of uncrystallizable short chains into the interfibrillar regions of the spherulites was also observed for PCL with M n = 1900. |
Author | Ou-Yang, Wen-Chung Hwang, Jenn Chiu Li, Lain-Jong Chen, Hsin-Lung Wong, Wen-Young |
Author_xml | – sequence: 1 givenname: Hsin-Lung surname: Chen fullname: Chen, Hsin-Lung – sequence: 2 givenname: Lain-Jong surname: Li fullname: Li, Lain-Jong – sequence: 3 givenname: Wen-Chung surname: Ou-Yang fullname: Ou-Yang, Wen-Chung – sequence: 4 givenname: Jenn Chiu surname: Hwang fullname: Hwang, Jenn Chiu – sequence: 5 givenname: Wen-Young surname: Wong fullname: Wong, Wen-Young |
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Copyright | Copyright © 1997 American Chemical Society 1997 INIST-CNRS |
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Keywords | Melt crystallization Kinetics Spherulites Experimental study Polycaprolactone Molecular weight property relation |
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Snippet | Poly(ε-caprolactone) (PCL) with a wide range of molecular weight (MW) has been prepared via fractionation by either precipitating PCL/chloroform solutions into... |
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SubjectTerms | Applied sciences Crystallization Exact sciences and technology Organic polymers Physicochemistry of polymers Properties and characterization |
Title | Spherulitic Crystallization Behavior of Poly(ε-caprolactone) with a Wide Range of Molecular Weight |
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