Solvent entrainment in and flocculation of asphaltenic aggregates probed by small-angle neutron scattering.
While small-angle neutron scattering (SANS) has proven to be very useful for deducing the sizes and masses of asphaltenic aggregates in solution, care must be taken to account for solvation effects within the aggregates so as to not err in the characterization of these important systems. SANS measurements were performed on solutions of asphaltenes dispersed in deuterated solvents in which a broad spectrum of solute and solvent chemical compositions was represented. Fits to the scattering intensity curves were performed using the Guinier approximation, the Ornstein-Zernike (or Zimm) model, a mass-fractal model, and a polydisperse cylinder model. The mass-fractal model provided apparent fractal dimensions (2.2-3) for the aggregates that generally decreased with increasing aggregate size, indicating increased surface roughness for larger aggregates. The polydisperse cylinder model provided typical values of the particle thicknesses from 5 to 32 angstroms, the average particle radius from 25 to 125 angstroms, and approximately 30% radius polydispersity. Subsequent calculation of average aggregate molar masses suggested a range of solvent entrainment from 30 to 50% (v/v) within the aggregates that were consistent with previous viscosity measurements. Additional calculations were performed to estimate the proportion of microparticle to nanoparticle aggregates in the solutions. The results indicate that the inclusion of solvation effects is essential for the accurate determination of aggregate molecular weights and fractal dimensions.
Gawrys
Keith L
KL
Department of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh, North Carolina 27965-7905, USA.
Blankenship
George A
GA
Kilpatrick
Peter K
PK