Rheology of polyaniline-dinonylnaphthalene disulfonic acid (DNNDSA) montmorillonite clay nanocomposites in the sol state: shear thinning versus pseudo-solid behavior

Abstract

The melt rheology of polyaniline (PANI)-dinonylnaphthalenedisulfonic acid (DNNDSA) gel nanocomposites (GNCs) with organically modified (modified with cetyl trimethylammonium bromide)-montmorillonite (om-MMT) clay has been studied for three different clay concentrations at the temperature range 120-160 °C. Field emission scanning electron microscopy (FE-SEM), wide angle X-ray scattering (WAXS), differential scanning calorimetry (DSC) and dc-conductivity data (~10⁻³ S/cm) indicate that the PANI-DNNDSA melt is in sol state and it is not de-doped at that condition. The WAXS data indicate that in GNC-1 sol clay tactoids are in exfoliated state but in the other sols they are in intercalated state. The zero shear viscosity (η₀), storage modulus (G') and loss modulus (G") increase than that of pure gel in the GNCs. The pure sol and the sols of gel nanocomposites (GNCs) exhibit Newtonian behavior for low shear rate (<6 × 10⁻³ s⁻¹) and power law variation for the higher shear rate region. The characteristic time (η) increase with increasing clay concentration and the power law index (n) decreases with increase in clay concentration in the GNCs indicating increased shear thinning for the clay addition. Thus the sols of om-clay nanocomposites of PANI-DNNDSA system are easily processible. The storage modulus (G') of GNC sols are higher than that of pure PANI-DNNDSA sol, GNC1 sol shows a maximum of 733% increase in storage modulus and the percent increase decreases with increase in temperature. Exfoliated nature of clay tactoids has been attributed for the above dramatic increase of G'. The PANI-DNNDSA sol nanocomposites behave as a pseudo-solid at higher frequency where G' and loss modulus (G'') show a crossover point in the frequency sweep experiment at a fixed temperature. The crossover frequency decreases with increase in clay concentration and it increases with increase in temperature for GNC sols. The pseudo-solid behavior has been explained from jamming or network formation of clay tactoids under shear. A probable explanation of the two apparently contradictory phenomena of shear thinning versus pseudo-solid behavior of the nanocomposite sols is discussed.