Journal of Rheology, Vol.45, No.3, 691-708, 2001
Linear and nonlinear theology of bidisperse polymer blends
We investigate linear viscoelastic properties and nonlinear stress relaxation dynamics in a series of bidisperse 1,4-polybutadiene blends. Blend systems comprising high- (ML) and low- (Ms) molecular weight polymers with M-L much greater than M-S > M-e are formulated in which the short polymer component functions as an ideal nonvolatile solvent for the long polymer chains. In blends with M-L approximate to 5 15x10(5) g/(mol) a critical molecular weight M-S* approximate to 4.8x10(4) g/(mol) is identified below whose terminal viscoelastic propel-ties are independent of Ms and vary with volume fraction of the long polymer molecules, phi (L), in a manner consistent with expectations for entangled polymer solutions. In blends with M-S > M-S* several approximate scaling relationships between terminal rheological properties and M-S can be determined from the experimental results, eta (0) similar to M-S(1.6), tau (d0) = eta (0)J(e)(0) similar to M-S(0), and tau (d,step) similar to M-S(1.6). The scaling exponents observed are consistent with earlier experimental reports, but disagree with theoretical predictions of the constraint release time in bidisperse melts. In agreement with previous step strain studies using entangled polystyrene reveal an unusual solutions, nonlinear step shear measurements using blends with M-S < M-S* short-time (1 < lambda (k)) crossing pattern in shifted nonlineal relaxation moduli G(t, gamma )h(gamma)(-1). The unusual short-time G(t, gamma )h(gamma)(-1) dynamics are first observed at phi (L) = 0.1 (N/N-e approximate to 13) and are accompanied by a continuous transition from type A to type C damping at long times, t > lambda (k). Our findings are consistent with the idea that type C damping is a characteristic feature of well entangled polymer systems and suggest that type A damping is just a special case of type C, applicable only in the limit of weakly entangled polymer chains.