T. Schneider and B. A. Wolf
"Solidification behavior of the theta system 2-propanol/poly(n-buthylmethacrylate) II. Dynamic-mechanical studies in the region of gelation"
Rheologica Acta 1995, 34, 172-181.
Abstract: Thermoreversible gelation of the system 2-propanol/poly (n-butyl methacrylate) - as detected by DSC or dielectric experiments - does not manifest itself in a straightforward manner in the dynamic-mechanical properties. Its occurrence can, however, be seen in many ways: i) For constant composition of the system and a reference temperature lower than T-gel, the storage modulus G' is larger than the loss modulus G'' in the glass transition zone of the master curve and both vary in an almost parallel manner with the angular frequency omega over almost two decades (whereas this feature is normally found for other gelling systems within the rubber plateau or the flow region). ii) The entanglement molecular weight obtained from G(max)'' is markedly less than the entanglement molecular weight in the melt divided by phi(2), the volume fraction of the polymer. iii) The temperature influences change from WLF-like to Arrhenius-like behavior as Tis lowered in the case of highly concentrated polymer solutions; analogous considerations hold true as phi(2) is increased at constant T. iv) For sufficiently low temperatures, the activation energy of flow exhibits a maximum in the concentration range where the gelation is - according to DSC experiments - most pronounced. Like with ordinary non-gelling systems it is possible to construct master curves. On the basis of Graessley's theory identical dependencies are obtained for the variation of the entanglement parts of the stationary viscosity with shear rate and for the dependence of the entanglement part of the complex viscosity on the frequency omega of oscillation. Zero shear viscosity and limiting value of the complex viscosity for vanishing omega as a function of phi(2) match smoothly and exhibit two points of inflection.
preprint number: 156