Many polymer and organic small-molecule thin films crystallize with microstructures that twist or curve in a regular manner as crystal growth proceeds. Here we present a phase-field model that energetically favors twisting of the three-dimensional crystalline orientation about and along particular axes, allowing morphologies such as banded spherulites, curved dendrites, and "s"- or "c"-shaped needle crystals to be simulated. When twisting about the fast-growing crystalline axis is energetically favored and spherulitic growth conditions are imposed, crystallization occurs in the form of banded spherulites composed of radially oriented twisted crystalline fibers. Due to the lack of symmetry, twisting along the normal growth direction leads to heterochiral banded spherulites with opposite twist handedness in each half of the spherulite. When twisting is instead favored about the axis perpendicular to the plane of the substrate and along the normal growth direction under diffusion-limited single-crystalline growth conditions, crystallization occurs in the form of curved dendrites with uniformly rotating branches. We show that the rate at which the branches curve affects not only the morphology but also the overall kinetics of crystallization, as the total crystallized area at a given time is maximized for a finite turning rate.
|Original language||English (US)|
|Journal||Physical Review E - Statistical, Nonlinear, and Soft Matter Physics|
|State||Published - Oct 15 2015|
All Science Journal Classification (ASJC) codes
- Statistical and Nonlinear Physics
- Statistics and Probability
- Condensed Matter Physics