Some connections between viscoelastic properties of PVC and plasticized PVC and molecular kinetics

Abstract

AbstractA coupling model that has been shown in the past to be capable of relating macroscopically measured relaxation parameters to molecular ones has been presented. In this article the coupling model is applied to the analysis of stress relaxation data collected by Cama and Sternstein on PVC and plasticized PVC. The Kohlrausch‐Williams‐Watts form, exp — (t/τ*)1−n, using n = 0.77 is found to be capable of describing the stress relaxation master curve at temperatures below the glass transition, Tg. From the temperature‐independent apparent activation energy found by Cama and Sternstein, the primitive activation energy of the α‐relaxation was calculated to be 7.5 kcal/mol, which is a reasonable value for the energy barrier to internal rotational isomerism in PVC. Support for this value is found from the data on two plasticized PVCs with different Tgs and apparent activation energies. By applying the coupling model in a similar manner, the primitive activation energies were found to be 8.5 kcal/mol for PVC plasticized with 6 pph dioctylphthalate and 7.7 kcal/mol for PVC plasticized with 6 pph tricresyl phosphate. Within experimental uncertainties, the three primitive activation energies can be considered to be the same. This finding is consistent with the physical basis for primitive activation energy and its identification with the internal rotation barrier, which should be independent of the type and amount of plasticizer in the system. Analysis of Cama and Sternstein's data on the effect of repeated stress aging on stress relaxation of quenched samples of PVC and plasticized PVC show that the coupling constant n increases systematically with each successive stress‐aging cycle until it approaches the value for slow‐cooled samples. These results are consistent with the notion that stress‐aging changes the structural state of the glass in ways similar to physical aging.