During sintering (coalescence) of aggregates of polydisperse primary particles (PPs), restructuring takes place, the average PP size increases and the PP size distribution (PPSD) narrows affecting particle performance in a number of applications. Here, aggregate sintering by viscous flow, lattice, and grain boundary diffusion is simulated by multiparticle discrete element methods focusing on PP growth dynamics and elucidating the detailed restructuring of aggregates during their coalescence. The effect of initial PPSD and sintering mechanisms on the evolution of PP polydispersity (geometric standard deviation) and surface area mean diameter are presented. Each sintering mechanism results in a distinct evolution of PPSD but quite similar growth in average PP diameter. Grain boundary diffusion has the strongest impact among all sintering mechanisms and rapidly results in the narrowest PPSD, as it has the strongest dependence on PP size. During sintering of aggregates with initially monodisperse PPs, the PPSD goes through a maximum width before narrowing again as PPs coalesce. A power law holds between projected aggregate surface area and number of PPs regardless of sintering mechanism and initial PP polydispersity. This law can be readily used in aerosol reactor design and for characterization of aggregates independent of material composition, initial PP polydispersity, and sintering mechanism.Theory Geometric models frequently describe sintering of agglomerates of PPs by viscous flow, 16,17 grain boundary, 18 and lattice diffusion. Such agglomerates are generated here by Correspondence concerning this article should be addressed to S. E. Pratsinis at pratsinis@ptl.mavt.ethz.ch.A grain boundary forms at the neck of nanoparticles in contact with two misaligned crystals. The high particle curvature in the neck induces a stress gradient resulting in a diffusive flux of atoms J from the neck center (source) to its surface (sink) 40
J5Dwhere dC v /dR is the vacancy concentration gradient, R the neck radius, C v the fraction of sites occupied by vacancies and X the volume of an atom or vacancy. During sintering by grain boundary diffusion, the atoms diffuse along the grain boundary ( Figure A1). 36