Steady State and Dynamic Oscillatory Shear Properties of Carbon Black Filled Elastomers

Abstract

A correlation between the steady shear viscosity and complex dynamic viscosity of carbon black (CB) filled rubbers was found by evaluating the Cox-Merz rule and an alternative approach originally proposed by Philippoff for dilute polymer solutions, but since applied to amorphous polymers and concentrated suspensions. This was done by measuring the rheological properties of 16 industrially important rubber mixes containing CB N660 at concentrations of 20 and 35% by volume. A capillary rheometer at various shear rates and a dynamic oscillatory shear rheometer at small and large amplitude oscillatory shear (SAOS and LAOS) were used. The apparent viscosity, storage and loss moduli, complex dynamic viscosity and Fourier transform harmonics were measured. Generally, the shear stress, storage and loss moduli increased with increasing CB loading. Also, the ratio of third and fifth stress harmonics to first harmonics increased with increasing strain amplitude and filler loading. Viscous Lissajous figures (shear stress versus shear rate) at a strain amplitude of 14% showed a nearly linear response for compounds containing CB at 20% by volume. All other shear stress responses demonstrated a strong nonlinearity. The stress waveforms at a strain amplitude of 140% for compounds containing 35% CB by volume displayed a backwards tilted shape expected for highly filled compounds. The stress waveforms at a strain amplitude of 1,000% tended toward a rectangular shape expected for pure polymer. Generally, the nonlinear response of the compounds appeared to be dominated by the filler at strain amplitudes of 14% and 140% and by the rubber matrix at a strain amplitude of 1,000%. The Cox-Merz rule was not applicable for any of the compounds with their complex dynamic viscosity being greater than the apparent viscosity. However, a modification of the approach proposed by Philippoff provided reasonable agreement between the apparent viscosity and complex dynamic viscosity.

Wall Slip-Free Viscosity Determination of Filled Rubber Compounds Using Steady-State Shear Measurements

“…This confirms the results of Hornig and Kielmann [22] for filled HNBR compounds and of Rauschmann [33] for an EPDM compound. Norton and Isayev [44] have shown this for carbon black-filled systems based on rubber polymers covering a wide range of chemical structures and molecular weights. In contrast, the ramp test method allows for the determination of viscosity data that are in good agreement with the corrected HPCR data.…”