Colloidal crystallization of poly(n-butyl acrylate) spheres in deionized aqueous suspension and the melting during dryness

Colloidal crystallization of poly(n-butyl acrylate) spheres (ammonium persulfate-poly(n-butyl acrylate) (APS-PBA), 320 ± 50 nm in diameter) was studied in deionized aqueous suspension. Coexistence of the crystal and distorted crystal structures was observed by the reflection spectroscopy. The critical concentrations of melting were ca. 0.01 and 0.03 in volume fraction in the presence of ion-exchange resins and in their absence, respectively. Crystal structures melted away during dryness by fusion of each spheres on the substrates, i.e., cover glass, watch glass, and Petri glass dish. Thickness profiles of the dried film changed sharply from the broad ring to the round hill as sphere concentration increased. The sharpness parameter S was evaluated from the ratio of the film size (diameter) against the full width at half maximum in the thickness profiles of the ring and/or the round hill. The S values decreased sharply from 30 to 1.2 as initial volume fraction of the spheres increased from 0.0005 to 0.1. The S values were significantly low compared with those of typical colloidal spheres, which supports the aggregate and/or fusion of the spheres resulting in their low convectional flow during dryness. The round hill profile at the high sphere concentration also supports that the fusion takes place easier during dryness. Microscopic observation of the dried film supports the formation of the homogeneous fused structures. It was clarified that colloidal crystallization of APS-PBA spheres takes place by the extended electrical double layers around the spheres like typical colloidal crystals of hard spheres. However, APS-PBA spheres are not so stable by the fusion especially at the high sphere concentrations and on the substrates.