Two-Step Process in Homogeneous Nucleation of Alumina in Supersaturated Vapor

Multiple pathways in crystal nucleation are now known to be more common than previously predicted; it is, therefore, crucial to understand the early stages of crystallization. Even in relatively simple vapor-phase homogeneous nucleation, the process has significant potential diversity. Here, we experimentally show crystalline Al 2 O 3 nanoparticles forming via precisely two steps in the nucleation process from supersaturated vapor with a moderate cooling rate. In situ FT-IR measurement of nucleation allowed us to observe the formation of Al 2 O 3 nanoparticles. Liquid-like particles first nucleated from the vapor before crystallizing. The crystalline phase was preserved by quenching without further transformation into the most stable α-Al 2 O 3 polymorph. The precipitated phase changed from δ-Al 2 O 3 for pure Al 2 O 3 to γ-Al 2 O 3 or θ-Al 2 O 3 by adding Sb or Cr, respectively. We demonstrate that a two-step process occurs in homogeneous nucleation of refractory materials from supersaturated vapor, which may facilitate polymorphic control in industry and improve understanding of cosmic dust formation in space.