Termination of Solid-State Crystal Growth in Molecular Glasses by Fluidity.
Fast crystal growth can abruptly emerge as molecular liquids are cooled to become glasses, a phenomenon presently unknown for other materials. This glass-to-crystal (GC) mode can cause crystallization rates orders of magnitude faster than those predicted by standard models. While GC growth is known for 12 systems, its features vary greatly with growth rates spanning a factor of 10(4). We report that the general condition for GC growth to exist is that liquid diffusion be slow relative to crystal growth according to D/u < 7 pm. This condition holds for all liquids exhibiting GC growth and suggests that the phenomenon is a solid-state process terminated by fluidity. GC growth must solidify several molecular layers before rearrangement by diffusion. We propose that GC growth propagates by a nonequilibrium crystal/liquid interface 3 nm wide that solidifies by local mobility. These results explain the prevalence of GC growth among organic liquids and guide its discovery in other materials.
School of Pharmacy and Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53705, United States.
Daniele
D
Musumeci
School of Pharmacy and Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53705, United States.
C Travis
CT
Powell
School of Pharmacy and Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53705, United States.
M D
MD
Ediger
School of Pharmacy and Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53705, United States.
Lian
L
Yu
amorphous; crystallization; diffusion; fluidity; glass; indomethacin; o-therphenyl; solid-state crystal growth