Effect of structure development on the rheological properties of PVDF/HNBR-based thermoplastic elastomer and its vulcanizates

The present work demonstrates the structure-rheology relationship of novel polyvinylidene fluoride/hydrogenated nitrile rubber blends with special reference to the effect of mixing time, which has not been amply discussed in the literature. In between 50 and 70 wt% rubber content, a yield in complex viscosity and secondary plateau in storage modulus were discerned due to interconnected droplets-matrix morphology manifesting the thermoplastic elastomeric nature of the blends (TPEs). Such network-like structure altered the rheological properties like relaxation time, capillary viscosity, die swell, elastic responses of the TPE with respect to the trend as expected according to the rule of mixing. Interestingly, in the early stages of mixing, when the dispersed size was bigger, the effect of physical network on the rheological properties was suppressed. During dynamic vulcanization (TPV), both lower and higher frequency responses in oscillatory shear flow, steady shear rheological properties, recoverable strain etc. have changed notably with mixing time. For example, although the complex viscosity of the TPV was higher at a lower frequency as compared to its TPE, it was significantly lower at a higher frequency at the beginning of dynamic curing; however, viscosity increased appreciably with time. Temperature-dependendent rheological properties were also influenced with mixing time of the compositions.