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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1779-1791 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphological character of uniaxially oriented poly(ethylene terephthalate) (PET) films was investigated as a function of draw ratio. Dynamic mechanical, infrared, and crystallite-size measurements were made on the samples. In addition, selective degradation experiments and molecular weight determinations were employed. The dynamic mechanical measurements indicated a sharp decrease in irregular folds for draw ratios of 3.0 and higher, which also coincided with the essentially complete disappearence of regular folds (from the 988 cm-1 band in the infrared spectra) in unannealed samples. Infrared studies of drawn samples annealed under different conditions gave evidence in support of a structure in which the chains are stretched out. Apparent crystallite-size measurements showed a sudden increase in length of the crystals in the direction of the draw beyond a draw ratio of 3.0. Molecular weight measurements showed a large increase in average chain length in the residue after selective degradation of amorphous material and folds; undrawn and slightly drawn samples gave a much lower Mn. Based on these observations, it is postulated that for higher draw ratios and present drawing conditions, the crystals are of the straight chain type, somewhat similar to the fringed-micelle crystal concept.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 1793-1801 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chain folding in unoriented poly(ethylene terephthalate) (PET) films has been investigated as a function of annealing time and temperature. To meet this objective dynamic mechanical, infrared, and molecular weight measurements were used, together with selective chemical degradation to remove chain folds and amorphous regions. The β dispersion in the dynamic mechanical spectrum of PET is here tentatively associated with motions of methylene and/or carboxyl groups in irregular chain folds; the β dispersion is not found in quenched amorphous polymer, in polymer where amorphous regions and chain folds have been removed, or in highly annealed PET where the irregular folds have regularized. Upon mild crystallization and annealing (30 min at 110°C) of initially amorphous film a large β dispersion appears and then diminishes upon further annealing at 220°C. As the β dispersion diminishes, the infrared regular fold band increases more than the crystallinity band, indicating regularization of folds. The molecular weight of the degraded residue corresponds approximately to typical fold-period dimensions (∼130 Å), and increases on annealing as expected from lamellar thickening. The degradation process has, by fold removal, reduced the chains in the crystals to a very short, uniform length.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 765-774 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To investigate the morphology of unoriented poly(ethylene terephthalate) (PET) films and the selective character of the aminolysis of PET, 67% crystalline polymer samples were degraded with 40% aqueous methylamine at room temperature. The aminolyzed PET samples were subjected to gel permeation chromatography (GPC), viscometry, electron microscopy, and small-angle x-ray diffraction (SAXD). Weight loss and density crystallinity measurements were also made.After 24 hr of aminolysis, the amorphous regions and chain folds were completely removed. The long molecular chains in the semi-crystalline polymer were reduced to monodisperse rods having a molecular weight of 1,800. The corresponding lamellar thickness was calculated to be 101 Å, consistent with the x-ray diffraction and electron microscope (EM) measurements. The EM photographs of “stripped” crystals show the lamellar structure previously found for other selectively degraded polymeric materials. The weight of crystalline debris remaining was consistent with the initial crystallinity. After degradation the crystallinity as determined by density was 96%.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 575-590 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The shrinkage of commercial oriented poly(ethylene terephthalate) filaments was studied within the framework of the kinetic theory of rubberlike elasticity. Previous workers had found that the shrinkage and optical behavior of amorphous polymers could be satisfactorily explained in terms of this theory. Such an analysis is now applied to semicrystalline samples of moderate and high draw ratios (from 2× to 6×).It was found in this work that the thermal shrinkage force behavior as well as the optical anisotropy as a function of stretch can be explained in terms of the theory of rubberlike elasticity, if the following reasonable assumption is made: the average number of statistical segments per network chain in the noncrosslinked sample increases as a function of the draw ratio. A possible mechanism for such behavior is the relaxation of some of the chain entaglements due to the strain imposed externally on the fiber.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 2057-2077 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(ethylene terephthalate) (PET), after certain thermal and mechanical histories, exhibits stress cracking when exposed to 40% aqueous methylamine. This reagent has also been used for selective degradation of PET films. Stress cracking is shown to occur during degradation only when a specimen supports an internal or externally applied stress, above a critical level. The cracking density in a filament is shown by the present work to increase as the draw ratio is increased or when the fiber is highly annealed. This increased cracking is associated with an increase in the magnitude of the internal residual stress resulting from molecular orientation developed during these processes. Because of this, crack density and fiber birefringence were found to correlate well. In addition, the geometry of the stress-cracking pattern along a filament is affected by internal residual stress since the propagation of spiral and helical cracks results from the effect of a biaxial stress field remaining at the filament surface after processing.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1935-1946 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several primary amines have been examined as selective degradative etchants for the investigation of poly(ethylene terephthalate) (PET) morphology. The objective is to remove less ordered regions, leaving crystals intact. The amines include 40% and 20% aqueous methylamine, 70%-40% aqueous ethylamine and pure and 40% aqueous n-propylamine. Weight-loss and x-ray diffraction data show that certain concentration of aqueous amine solution simultaneously degrade and crystallize PET. This observation indicates the hazard of using some of these amine reagents to characterize PET morphology since the crystalline structure found after etching is likely to be a result of solvent-induced crystallization during degradation. Data for 40% aqueous methylamine used at room temperature shows that crystallization does not occur during etching, and in light of earlier research indicates the favorable nature of this reagent as a selective degradative medium for PET. Application of this reagent disclosed that in oriented PET fibers chemical stress cracking occurs, causing the degradative reagent to lose its selectivity.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1773-1781 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Either of the two endothermic melting peaks found by differential thermal analysis of nylon 66 may be converted to the other by appropriate choice of annealing conditions. The two peaks are considered due to the melting of two morphological species, forms I and II. Form I is relatively fixed in melting temperature, while the form II melting temperature varies with annealing conditions and can be either above or below form I. The two forms can be distinguished by whether or not the conversion I → II takes place; if the sample is in form II no change in the thermogram is observed under suitable conversion conditions. The conversion of form I to form II also takes place during cold drawing. It has been previously shown that form I results from rapid cooling from the melt, and form II results from slow cooling. Form I appears to be kinetically favored, while form II is thermodynamically preferred. The variability in the form II melting point is attributed to variable crystal size and/or perfection.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1033-1057 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phenomenon of double melting, as manifested by two characteristic endotherms in the melting region on a differential thermal analysis (DTA) scan, has been studied in nylon 66 and polystyrene as a function of sample treatment by annealing or drawing. A variety of techniques were used in these studies including DTA, x-ray diffraction, electron microscopy, and mechanical testing. It is shown that the two endotherms are not caused by a bimodal crystal size distribution, by recrystallization, by orientation changes, or by phase changes. It is proposed that one endotherm is caused by the melting of foldedchain crystals, while the other is due to the melting of less perfect bundle crystals. This view is well supported by the results, especially by the DTA measurements made at different heating rates. Published data on the thermal behavior of annealed and drawn poly(ethylene terephthalate) and on polyethylene crystallized at various pressures may also be explained on this basis if it is allowed that in polyethylene the chains may be more extended.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 10 (1972), S. 1273-1283 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The two endotherms found during DSC analysis of annealed or drawn poly(ethylene terephthalate), PET, are discussed in greater. detail. Earlier workers proposed that the endotherms were the result of separate morphologies, i.e., extended-chain and folded-chain crystals, but more recently Roberts and others have presented data on the effect of DSC heating rate on annealed PET endotherm areas which indicate that the higher temperature endotherm is the result of recrystallization in the DSC. The present work explains the reasons for recrystallization, and presents data showing that samples cooled at various rates from the melt also exhibit recrystallization in the DSC, in much the same manner as samples annealed for different lengths of time. Further, by prolonged annealing before analysis, part of the recrystallization exotherm can be observed in the DSC scan. Drawn nylon 66 also exhibits recrystallization in the DSC, in a manner similar to annealed or slowly crystallized PET. The amount of material that recrystallizes is determined by the time and supercooling available between first melting and the ultimate recrystallization temperature, i.e., a temperature at which there is too little time and temperature driving force for further recrystallization to occur. Infrared absorption data show an increase in “regular” fold content during prolonged annealing of PET, while dynamic mechanical data show a marked decrease in a dispersion that is likely associated with the looser fold crystal morphologies. Annealed PET does superheat in the DSC, leaving unanswered the question as to whether any partially extended material is present along with the regular-fold material. For cold-drawn PET, the infrared data indicate disappearance of regular folds and the dynamic mechanical data indicate disappearance of the looser folds. Cold-drawn PET also superheats. These data indicate a likelihood of at least partially extended morphologies in cold-drawn PET; these observations do not apply to PET drawn at high temperatures or to polyethylene.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 437-445 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic mechanical properties of a series of epoxy polymers of known network structure have been investigated. It was shown that the distance between crosslinks could be predicted from either the shift in the glass transition temperature Tg or by use of the dynamic modulus above Tg. The front factor in the equation of state for rubber elasticity was near unity for stoichiometric equivalence of epoxy and amine and increased slowly with excess of either component.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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