Oxidative Stabilization of Acrylic Fibers. I. Oxygen Uptake and General Model.
MASSACHUSETTS INST OF TECH CAMBRIDGE DEPT OF MATERIALS SCIENCE AND ENGINEERING
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The mechanism of oxidative stabilization of acrylic fibers is characterized by two limiting cases which are determined by the fiber chemistry, the reaction conditions, and the diameter of the filament. These limiting cases correspond to diffusion-limited and reaction-limited kinetic processes. Although the chemistry of stabilization is too complex to specify, the various reactions are separated into two categories those which occur prior to or concurrently with polymerization of the nitrile groups, called prefatory reactions and those which occur subsequent to nitrile polymerization, called sequent reactions. Under conditions which allow the prefatory reactions to occur significantly before the sequent reactions, the diffusion of oxygen to reactive sites is limited by previously oxidized material and the fiber shows a typical two-zone morphology. Under conditions where the prefatory and sequent reactions occur sequentially, the overall stabilization process is limited by the rate of the prefatory reactions but a skin is established at the fiber surface which acts as an oxygen barrier. Data from a variety of sources, including oxygen analysis, microscopic examination, fiber residue after etching, tension developed in fibers held at constant length, and small angle X-ray patterns, are cited as evidence for the two limiting cases. Author
- Polymer Chemistry