By C. H. Bamford
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Extra resources for Degradation of Polymers: Free Radical Polymerization (Comprehensive Chemical Kinetics)
Each of them can be analysed according to the various methods given below. In favourable cases, determination of reaction order, global activation energy and frequency factor is rapid and easy. Thus, for reactions of the tY Pe A(so1id) - B(so1id) + C(gas) the variation of weight per unit temperature depends on the rate of heating, weight and temperature according t o dW R T = - - - - ( A / R H )e-EIRT W" dT where W is the weight of active material, RH is the rate of heating, T is the temperature, A is the frequency factor, E is the activation energy and n is the reaction order.
Dynamic thermogravimetric methods offer many advantages when compared with the usual isothermal methods. The thermal behaviour of a polymer can be characterized rapidly over a wide range of temperature in one experiment using a small amount of sample. When the rate of heating is kept constant, the TGA trace is a simple sigmoidal curve for many polymers (Fig. 14). This of course implies that the degradation mechanism does not change with temperature. If concurrent reactions are occurring, the traces may be very complicated and impossible to analyse.
X/xo,plotted against conversion, l-M, IMP. Fig. 8. Random chain scission, initial “most probable” distribution [ 191. , (1/y)/x0. References p p . 165-1 73 20 Kinetics including transfer and the effect of molecular weight will not be discussed. Some of the conclusions are summarized in Fig. 9*. xO(ks + k * R )t Fig. 9. Random chain scission initiation, initial “most probable” distribution [ 191. The effect of chain transfer on weight remaining against time. , (l/y)Ixo. At each zip length ratio, curves forJhree-values of the fraction of the initial weight loss rate due to chain transfer, F = k I R / ( k l R + k s ) , are plotted.