화학공학소재연구정보센터
Journal of Rheology, Vol.44, No.6, 1363-1384, 2000
Nonlinear rheology of immiscible polymer blends: Step strain experiments
Relaxation experiments after simple shear flow were performed on (50/50) PB/PDMS poly(1-butene)/polydimethylsiloxane immiscible model blends and the results were compared to the predictions of the Doi-Ohta and Lee-Park models. Three situations of flow were examined: (i) first the variation of stress relaxation was followed in time at various step strain amplitudes, (ii) variation of stress relaxation as a function of the amplitude of preshear rate at a fixed strain, and (iii) at a fixed strain and preshear rate, the relaxation of the stress was studied as a function of the time elapsed between the end of the preshear and the step strain. After application of step strains of various magnitudes, the stress relaxation modulus G(t,gamma) at short times was found to obey the Wagner time-strain separability [Wagner (1976)]. It was possible to separate linear effects from the nonlinear ones via a damping function h( gamma) of sigmoidal form. After cessation of steady shear flow of different magnitudes, the linear stress relaxation modulus at long time scale was found to be very sensitive to the shear flow conditions and to the elapsed time between the end of the preshear and the step strain. The morphology evolution characterized by the droplet radius extracted from emulsion models as a function of the steady shear rate was found to be fairly described by the empirical partially mobile interface coalescence model and did not obey the inverse proportionality to shear rare as predicted by the Doi-Ohta theory. After cessation of steady shear flow, the blend morphology continues to evolve until a steady state was reached. Two kinetics seem to govern the establishment of a stable morphology: a rapid retraction process of elongated droplets leading to an increase of terminal relaxation time followed by breakup via Rayleigh instabilities and end-pinching mechanisms as was confirmed by in situ morphological observations carried out between two sliding plates at equivalent deformation.