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Note that the quantum yields increased with increasing stress, reached a maximum, and then decreased As discussed above, such a plot is predicted by the DRRE hypothesis (Fig 2b) A key tenet of the DRRE hypothesis is that stress eventually causes ordering of the amorphous polymer chains, and this ordering causes a decrease in the quantum yields (or rates) of the polymer decomposition X-ray scattering and IR spectroscopy are both commonly used to assess crystallinity in PVC,91 95 and both techniques clearly showed that stress increased the chain ordering in polymer 3 In the case of IR spectroscopy, an increase in the absorbance ratio of the infrared peak at 635 638 to that at 610 615 cm 1 indicates an increase in crystallinity;94,95 and this ratio did, in fact, increase with increasing stress.

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Integration from 0 to the reactor length L and from 0 to XA(L) leads to the well-known dimensionless mass balance of the PFTR:

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In the case of wide-angle x-ray diffraction, an increase in intensity of the (200) and (110) re ections (in the 16 18 2 region91 93) has been shown to correlate with an increase in crystallinity in PVC Experiments showed that these peaks grew in and increased in intensity with increasing stress, again consistent with the conclusion that stress is increasing the chain ordering in polymer 3 Additional mechanistic evidence consistent with the DRRE hypothesis was sought to con rm this interpretation on the role of stress, and for that reason the experiments described above were repeated with plasticized polymer 3 Because chain movements are more facile in plasticized polymer, it was predicted that, at any given stress, the quantum yields for degradation should be higher (because it is easier for the radicals to separate from each other, which lowers their probability of recombination).

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In addition, the maximum in the curve shown in Figure 3 should occur at a lower stress because chain alignment is easier Polymer 3 was plasticized by blending it with dioctyl phthalate (DOP) As expected, the presence of the plasticizer decreased the glass transition temperature (Tg) of the polymer to 25 C from 65 C As likewise expected, the DOP plasticizer resulted in a decrease in the tensile strength and yield stress of the polymer and a longer elongation A plot of quantum yield for degradation vs tensile stress for plasticized polymer 3 matched the predictions of the DRRE hypothesis that is, stress initially caused an increase in degradation e ciency to some maximum value, at which point the quantum yields started to decrease Thus, for a given stress, the quantum yields of degradation were higher for plasticized polymer than for 3.

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approach to modeling granule coalescence mechanisms, AIChE J., 1997, 43 (4), 927 934. A. A. Adetayo, J. D. Litster, S. E. Pratsinis, et al., Population balance modeling of drum granulation of materials with wide size distribution, Powder Technol., 1995, 82, 37 49. M. Banks, M. E. Aulton, Fluidised-bed granulation: A chronology, Drug Dev. Indust. Pharm., 1991, 17 (11), S1437 S1463. H. D. Baehr, Thermodynamik, 8. Auflage, Springer-Verlag, Berlin-Heidelberg-New York, 1994. R.-D. Becher, Untersuchungen der Agglomeration von Partikeln bei der Wirbelschicht-Spr hgranulation, VDI Fortschritt-Berichte, Reihe 3, Nr. 500, VDI Verlag, D sseldorf, 1997. W. A. Benesch, 850 C Theorie und Praxis der Wirbelschichtfeuerung, VDI Berichte, Nr. 1492 (1999), S145 S152. J. Beranek, K. Rose, G. Winterstein, Grundlagen der Wirbelschichttechnik.

In addition, the maximum in the curve occurred at a lower stress compared to that in.

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