Our simulations of polymer crystallization from solutions show that (1) entropic barriers control the selection of the initial lamellar thickness, (2) growth at the crystalline interface is chain adsorption followed by crystallographic registry, and (3) lamellar thickening is a highly cooperative process requiring the mobility of all chains in the crystal. These results, especially the latter, challenge the conventional Lauritzen-Hoffman theory and its generalizations.

• Received 10 May 2001

DOI:https://doi.org/10.1103/PhysRevLett.87.218302