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  • 1970-1974
  • 1965-1969  (2)
  • 1965  (2)
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  • 1970-1974
  • 1965-1969  (2)
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  • 1
    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: It is well known that the rheological behavior of polyethylene melts is affected by at least four variables: (1) molecular weight, (2) molecular weight distribution, (3) long-chain branching and its distribution, and (4) short-chain branching. Of these, the first three appear to have the largest effects. In the present paper an attempt is made to determine the effect of molecular weight distribution by rheological studies of polymers having similar molecular weight distribution by rheological studies of polymers having similar molecular weights and degrees of branching, but varying considerably in their molecular weight distributions as determined by fractionation. The rheological parameters studied were melt recovery, non-Newtonian behavior, critical shear rate, and melt strength. It is shown that the melt recovery increases uniformly as the molecular weight distribution broadens. The degree of non-Newtonian behavior, as measured by the exponent n of the power law, also increases with distribution breadth and is particularly affected by the amount of low molecular weight polymer present. Melt strength increases in a similar manner. Critical shear rate is inversely related to the breadth of the molecular weight distribution and is particularly dependent on the molecular weight of the highest fractions. The log of the critical shear rate is inversely proportional to the melt index recovery.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    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: Studies of the rheological properties of fractions of linear and branched polyethylenes have shown that the melt recovery of linear polyethylene fractions is very small and independent of molecular weight over a wide range. Fractions containing high degrees of long-chain branching, on the other hand, have high melt recoveries. The melt recovery of a fraction can therefore be used as an index of long-chain branching. Alternatively, if no long-chain branching is present, the melt recovery is a unique function of the molecular weight distribution. This effect is illustrated by blends of fractions. The log of the critical shear rate is a linear function of the log melt viscosity of the fraction for both linear and branched polyethylenes. This would indicate that the critical shear rate of polydisperse samples would depend primarily on the weight-average of Z-average molecular weight of the polymer. This is confirmed by previous studies on polydisperse samples. It also appears that critical shear rate is highly dependent on the homogeneity of the sample. Blends of the same fractions had quite different critical shear rates, depending on the procedure used to prepare them, even though their molecular weight distributions were identical. The change in viscosity with shear rate is not a unique function of molecular weight or melt viscosity. Fractions of linear polyethylene show a greater change in viscosity with shear rate than branched fractions of similar low shear melt viscosity. This suggests that the effect is related to chain entanglement or coordinated segmental motion.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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