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Thermal Degradation vis-a-vis Thermal Volatilisation of High Polymers
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Random thermal degradation behaviour of long chain polymers has been studied in detail from the consideration of kinetics of dissociation of bonds vulnerable to thermal activation. In the process, thermogravimetric equations correlating kinetic parameters of the degradation reaction have been developed. Different experimental techniques for evaluation of kinetic parameters have also been devised. An analysis of the results reveals that thermogravimetric weight-loss can be expressed as a Freeman-Carroll type first order reaction having a rate constant that varies over a wide range with the progress of the reaction. High initial molecular weight and high molar cohesion impart retarding influences on thermal volatilisation. Interestingly, the isothermal volatilisation rate is found to pass through a maximum which provides a clue to determination of the kinetic parameters of the degradation reaction.
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