Multilevel structure of reinforcing silica and carbon

Abstract

Using small-angle x-ray (SAXS), neutron (SANS), x-ray diffraction and light scattering, we study the structure of colloidal silica and carbon on length scales from 4 Å < q −1 < 107 Å where q is the magnitude of the scattering vector. These materials consist of primary particles of the order of 100 Å, aggregated into micron-sized aggregates that in turn are agglomerated into 100 µ agglomerates. The diffraction data show that the primary particles in precipitated silica are composed of highly defective amorphous silica with little intermediate-range order (order on the scale of several bond distances). On the next level of morphology, primary particles arise by a complex nucleation process in which primordial nuclei briefly aggregate into rough particles that subsequently smooth out to become the seeds for the primaries. The primaries aggregate to strongly bonded clusters by a complex process involving kinetic growth, mechanical disintegration and restructuring. Finally, the small-angle scattering (SAS) data lead us to postulate that the aggregates cluster into porous, rough-surfaced, non-mass-fractal agglomerates that can be broken down to the more strongly bonded aggregates by application of shear. We find similar structure in pelletized carbon blacks. In this case we show a linear scaling relation between the primary and aggregate sizes. We attribute the scaling to mechanical processing that deforms the fractal aggregates down to the maximum size able to withstand the compaction stress. Finally, we rationalize the observed structure based on empirical optimization by filler suppliers and some recent theoretical ideas due to Witten, Rubenstein and Colby.