Shear-induced aggregation and break up of fibril clusters close to the percolation concentration

Abstract

To probe the behaviour of fibrillar assemblies of ovalbumin under oscillatory shear, close to the percolation concentration, c_p (7.5%), rheo-optical measurements and Fourier transform rheology were performed. Different results were found close to c_p (7.3%), compared to slightly further away from c_p (6.9 and 7.1%). For 6.9 and 7.1%, a decrease in complex viscosity, and a linear increase in birefringence, Δn′, with increasing strain was observed, indicating deformation and orientation of the fibril clusters. For 7.3%, a decrease in complex viscosity was followed by an increase in complex viscosity with increasing strain, which coincided with a strong increase in Δn′, dichroism, Δn″, and the intensity of the normalized third harmonic (I₃/I₁). This regime was followed by a second decrease in complex viscosity, where Δn′,Δn″ and I₃/I₁ decreased. In the first regime where the viscosity was decreasing with increasing strain, deformation and orientation of existing clusters takes place. At higher oscillatory shear, a larger deformation occurs and larger structures are formed, which is most likely aggregation of the clusters. Finally, at even higher strains, the clusters break up again. An increase in complex viscosity, Δn′, Δn″ and I₃/I₁ was observed when a second strain sweep was performed 30 min after the first. This indicates that the shear-induced cluster formation and break up are not completely reversible, and the initial cluster size distribution is not recovered after cessation of flow.