Various modes of void closure during dry sintering of close-packed nanoparticles

Film formation from aqueous suspensions of polymer nanoparticles is an important process in many environmental friendly applications and particularly for waterborne coatings. This process occurs via three mains steps: concentration, sintering, and interdiffusion. During the sintering step, the particles in close-packed morphology deform and the interstices between them close under Laplace pressure. This step is crucial in the film formation process since it is where the suspension turns into a uniform defect-free film. Most of the experimental and theoretical studies on sintering assume that the interstices close uniformly over the entire film. We use small-angle neutron scattering to probe void closure between polystyrene nanoparticles. We show that the voids close simultaneously and uniformly throughout the annealing process in large particles. For particles with a diameter smaller than 60 nm, we interpret the results to show that the interstices close heterogeneously at the nanoscopic level: in the beginning of annealing, some interstices close while others enlarge, and eventually they all vanish. The difference between the behavior of large and small particles is related to the high polydispersity of small particles compared to the larger ones.