Orientational changes in crystalline polychlorotrifluoroethylene copolymer films

Adams, G. C.; Stein, Richard S.

doi:10.1002/pol.1967.110050701

J. Polym. Sci. B Polym. Lett.

1967

DOI: 10.1002/pol.1967.110050701

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Orientational changes in crystalline polychlorotrifluoroethylene copolymer films

G. C. Adams

Richard S. Stein

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Cited by 5 publications

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Some studies of the crystallization of polychlorotrifluoroethylene copolymer films

Adams

Stein

1968

J. Polym. Sci. A‐2 Polym. Phys.

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A fluorocarbon copolymer of chlorotrifluoroethylene (96%) and vinylidene fluoride has been isothermally crystallized and the quenched films analyzed by the light microscope, photographic light‐scattering, and density measurements. Above a supercooling of 79°C., homogeneous nucleation dominates, giving a morphology that appears to be that of a twisted ribbon. At supercoolings below 79°C., heterogeneous nucleation dominates and leads to spherulitic morphology. Sheaf or rodlike morphology occurs at very low supercoolings. Crystallization rates determined from density measurements at room temperature indicate maximum rate due to heterogeneous nucleation occurring at a supercooling greater than 79°C., but the temperature for maximum rate cannot be identified because of the transition to homogeneous nucleation which causes a discontinuity in the rate versus temperature curve. Superposability of crystallization isotherms constructed from density values are inconsistent with the large melting point lowering from that of polychlorotrifluoroethylene for this copolymer. However, this may be explained by the presence of a different crystal system for each monomer in the copolymer.

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Some studies of the crystallization of polychlorotrifluoroethylene copolymer films

Adams

Stein

1968

J. Polym. Sci. A‐2 Polym. Phys.

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Crystal and amorphous orientation behavior of poly(chlorotrifluoroethylene) films in relation to crystalline superstructure

Hashimoto

Kawasaki

Kawai

1978

J. Polym. Sci. Polym. Phys. Ed.

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The relationship between the crystalline superstructure of polymer films and molecular orientation was studied in cold‐drawn poly(chlorotrifluoroethylene) films by wide‐angle x‐ray diffraction, birefringence, and depolarized light scattering. By changing crystallization conditions, specimens with almost identical crystallinity but different crystalline superstructures were obtained; i.e., (1) a structure having a random array of crystallites, (2) a superstructure having a rod‐like orientation correlation of the chains (a prespherulitic and sheaf‐like superstructure), and (3) spherulitic superstructure. Upon stretching of specimens, crystallites initially randomly arranged orient with their chain axes along the stretching direction in accord with simple affine deformation. The amorphous chains also orient along the stretching direction. The orientation behavior of the specimens having the rod‐like superstructure is similar to that of the specimens with a random array of crystallites, indicating that the interaction between the crystallites in the superstructure is relatively weak. The molecular orientation behavior of the spherulitic specimens, however, strongly deviates from simple affine deformation owing to strong interaction of the crystallites in the spherulites. The deviation can be interpreted in terms of spherulite deformation and of internal reorientation of chains within deformed spherulites.

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Stress‐induced crystallization of poly(ethylene terephthalate)

Misra

Stein

1979

J. Polym. Sci. Polym. Phys. Ed.

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Quenched amorphous films of poly(ethylene terephthalate) (PET) are stretched at temperatures less than Tg; changes in density, wide‐angle x‐ray diffraction, and small‐angle light scattering are observed. The density increase upon stretching is attributed to an increase in crystallinity accompanied by an increase in the intensity of somewhat diffuse wide‐angle x‐ray diffraction and of both VV and HV small‐angle light scattering patterns. The formation of oriented rodlike superstructure may be discerned from small‐angle light scattering. Annealing of these samples increases the crystallinity as measured from density and leads to an increase in the perfection of crystalline and supercrystalline structure as measured by wide‐angle x‐ray diffraction and small‐angle light scattering. The rodlike morphology changes to form spherulitelike aggregates as observed by small‐angle light scattering and light micrographs. A model is proposed to explain the observations. Studies are extended to stretching films of PET above their Tg and observing changes in birefringence, density, wide‐angle x‐ray diffraction and small‐angle light scattering as a function of elongation and stretching temperature. The formation of defomed spherulitelike superstructure may be discèrned from light micrographs. Results are compared with those obtained upon stretching films below Tg.

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Orientational changes in crystalline polychlorotrifluoroethylene copolymer films

Cited by 5 publications

References 8 publications

Some studies of the crystallization of polychlorotrifluoroethylene copolymer films

Some studies of the crystallization of polychlorotrifluoroethylene copolymer films

Crystal and amorphous orientation behavior of poly(chlorotrifluoroethylene) films in relation to crystalline superstructure

Stress‐induced crystallization of poly(ethylene terephthalate)

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