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• W1967783460 abstract "Polymer chains undergo degradation through a variety of mechanisms, including shear action, chemical attack, thermal activation, electromagnetic (γ, UV) and ultrasonic irradiation. In many macromolecular systems, the breaking of bonds does not occur randomly but depends upon the position within the chain and the total chain length. Before the advent of GPC, the distribution of bond scission probability along the chain could only be inferred from the evolution of some molecular weight (MW) average as a function of extent of degradation. Over the past few years, gel permeation chromatography has evolved as a reliable analytical tool to measure not only the different MW averages, but also the molecular weight distribution (MWD) of the degraded samples. Obviously, the possibility of determining change, over the whole MWD, gives more insight into the mechanisms involved than do MW averages. The information content of the GPC traces could, however, be usefully exploited, but only after extensive data treatment. The general procedure starts with the elaboration of a degradation scheme and the integration of the corresponding set of differential kinetics equations. The rate constants were then used as fitting parameters until good agreement was obtained between the calculated MWD and the experimental curves. Case studies taken from the field of mechanochemical degradation are presented to illustrate the possibilities and limitations of the technique. In one instance, during the freezing-and-thawing degradation of polystyrene, it is found that good concordance between calculations and experiments could only be obtained if ternary bond scission is included in the degradation scheme. The formalism developed for single scission kinetics is extended to the case of a concerted multiple fracture process." @default.
• W1967783460 created "2016-06-24" @default.
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• W1967783460 date "1994-01-01" @default.
• W1967783460 modified "2023-10-15" @default.
• W1967783460 title "Kinetics of mechanochemical degradation by gel permeation chromatography" @default.
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• W1967783460 doi "https://doi.org/10.1016/0141-3910(94)90114-7" @default.
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