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  • Polymer and Materials Science  (6)
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 31 (1986), S. 1619-1629 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A comparison of water sorption and diffusion behavior in 2 mil, as-received, Kapton= Trademark of E.I. Dupont de Nemours Inc. film, and in otherwise identical but hygrothermally aged samples, suggests chemical differences between the samples. These differences can be related to known polyimide chemistry and the specific history encountered by the samples. Although the sorption isotherms are similar for an as-received 0.3 mil sample studied earlier and for the as-received 2 mil samples studied here, the diffusion coefficient of water in the as-received 2 mil sample is approximately 300% larger than in the as-received 0.3 mil sample. This large effect is believed to be related to the presence of small, paracrystalline aggregates with large aspect ratios. Differences in orientation measured by birefringence for the two samples suggest that the barrier properties of Kapton® are strongly affected by the detailed morphological organization of the ordered aggregates. Comparison of the sorption isotherms for the as-received and hygrothermally aged 2-mil films suggests a significant increase in the hydrophillic nature of the aged film. This change is consistent with an apparent chemical reaction between water and uncyclized amic acid residues in the film. The tendency for water to cluster in as-received Kapton® is essentially eliminated by the chemical modification associated with hygrothermal aging. The hygrothermal aging produces a dramatic reduction in the water vapor diffusion coefficient at low vapor activities but a rather modest change at high activities.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 27 (1989), S. 1837-1851 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rheological behavior and fiber spinning are investigated for the Celanese liquid crystal copolyester 30 mol% p-hydroxybenzoic acid and 70 mol% 2-hydroxy-6-naphthoic acid (designated as 30HBA/70HNA) with inherent viscosity 7.8 dL/g. Shear thinning viscosity, and yield stress are observed at low shear stress, which probably results from the existence of crystallites in the melt.The crystal-nematic melting point of the copolymer, as measured by differential scanning calorimetry, is around 309°C. Extrudates are collected at four different temperatures ranging from 315 to 345°C. Melt fracture and die swell are observed above 335°C at low shear stress. A wide-angle x-ray diffraction (WAXS) study of an annealed sample indicates that the abnormal phenomenon may be due to crystallites arising from blocky units of HNA. Fiber spinning is performed at high shear rate at 325 and 335°C. Flow is stable under these conditions. The spin draw ratio is the ratio of take-up velocity to the velocity of extrudate existing from the capillary. The initial modulus reaches a maximum at a fairly low spin draw ratio. Instron and wide-angle x-ray (WAXS) studies show that the mechanical properties and orientation are poor for the fiber spun near the crystal-nematic melting point. Also, thermal history is found to affect the rheological behavior. Heat treatment offibers, particularly those which are well oriented, brings an improvement of mechanical properties.
    Additional Material: 19 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 26 (1988), S. 1711-1725 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have investigated the rheological properties of the Celanese copolyester with the composition 75 mol% p-hydroxybenzoic acid and 25 mol% 2-hydroxy-6-naphthoic acid (designated as 75HBA/25HNA). Three different samples having inherent viscosities 3.0, 6.0, and 9.2 dL/g were studied. A flow instability is observed at low shear stress which produces an irregularity in the fiber diameter. The surface irregularity becomes less pronounced above a minimum shear stress, indicating that the flow instability originates in the capillary. For these nematic melts, the minimum shear stress marking the onset of more regular flow is found to decrease with increasing temperature and with decreasing inherent viscosity of the copolyester. The die swell ratio of extrudates decreases with increasing shear stress. Fibers were spun from the samples having ηinh = 9.2 and 3.0 dL/g. The initial modulus and tenacity to break for 75HBA/25HNA fibers spun at sufficiently high shear stress to produce smooth filaments are significantly lower than the values we previously reported for fibers of the 58HBA/42HNA copolyester. Moreover, the optimum properties are obtained at relatively low spin-draw ratios. The 75HBA/25HNA polyester also exhibits a yield stress which decreases with increasing temperature. This observation indicates the presence of crystallities at the test temperatures. We believe that the higher content of HBA in the present copolymer gives rise to crystallization of HBA blocks in the thread line and that defects are introduced at higher spin-draw ratios which cause the mechanical properties to become worse.
    Additional Material: 16 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 24 (1986), S. 779-792 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sorption kinetics and equilibria as well as permeabilities and diffusion time lags for CO2 in Kapton polyimide film have been studied at temperatures from 35 to 55°C and pressures up to 0.78 atm. The sorption/desorption cycles indicate that the diffusivity of CO2 increases with increasing local penetrant concentration in the polymer. Both the permeability and time lag decrease with increasing upstream CO2 pressure. All of these results are described well by theoretical expression based on the dual-mode theory of sorption and transport in glassy polymers.
    Additional Material: 11 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 27 (1989), S. 819-835 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rheological behavior of the thermotropic liquid crystal copolyesters composed of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid (indicated as HBA/HNA) is investigated for three different compositions: 75:25, 58:42, 30:70 (in mol%). The inherent viscosities are 9.2, 5.1, and 7.8 dl/g, respectively. Yield stress is observed for all three samples. This indicates the existence of crystallites in the melt which may be related to the shear thinning viscosity at low shear stress. Melt fracture, and a die swell ratio which increases with shear rate, are also observed at higher temperatures and at low shear stress for the two copolyesters having compositions 75:25 and 30:70. We have also estimated for 30HBA/70HNA at 335°C the entrance pressure loss, Δpent, and ΔPent/δw, where δw is the shear stress at the capillary wall. The large value of ΔPent/δw suggest that HBA/HNA is a highly elastic polymeric material. It is found that both ΔPent and ΔPent/δw increase with shear rate. However, the high elasticity does not account for the disappearance of melt fracture and contraction of die swell at high shear stress. This abnormal phenomenon is ascribed to the formation of a network of crystallites caused by blocky regions in the copolymer.
    Additional Material: 18 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 30 (1985), S. 1035-1047 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Sorption isotherms and diffusion coefficients of water in a 0.3-mil Kapton polyimide film at 30, 45, and 60°C are reported. The data are well described by the dual mode sorption and transport models at low activities. At high penetrant activities, clustering of water is suggested by a Zimm-Lundberg analysis of the sorption data and the fact that the diffusion coefficient for water decreases with increasing external vapor activity. The effect of temperature on the diffusion coefficients at infinite dilution and the dual mode sorption parameters kD, b, and CH′ are presented and discussed. The magnitude of the activation energy of the diffusion coefficient at infinite dilution, 5.4 kcal/mol, is smaller than the corresponding activation energy in more flexible chain polymers, perhaps suggesting that rather small backbone motions are associated with diffusion of water through the Kapton matrix. The predictions for the isosteric enthalpy of sorption from the dual mode model are presented and compared with the values determined from graphical analysis of the sorption isotherms performed independently without reference to the dual mode sorption model.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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