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Application of degradation kinetics to the rheology of poly(hydroxyalkanoates)
Authors:Graham M Harrison  David H Melik
Abstract:The time‐dependent rheological behavior of a series of 3‐hydroxybuytrate‐based semicrystalline copolymers is employed to determine the expected rheological curves that would be generated in the absence of any polymer degradation. Both dynamic frequency sweep and shear rate sweep experiments were analyzed. A model for the degradation kinetics, coupled with standard rheological relationships, was employed to extrapolate the measured sweeps to predicted curves at time zero, prior to degradation. The model is broadly applicable over a wide range of frequencies or shear rates, and generates a single degradation rate constant k for each polymer studied. A similar, although ad hoc, procedure was applied to the dynamic storage and loss moduli. The model provides a method for determining the rheological behavior of degrading polymers over a time interval, typically found in processing applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1794–1802, 2006
Keywords:polymer degradation  rheology  kinetics  PHA
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