Spontaneous and Inductive Thickenings of Lamellar Crystal Monolayers of Low Molecular Weight PEO Fractions on Surface of Solid Substrates

Crystalline macromolecules form folded-chain lamellar and metastable crystals. Annealing at a temperature below melting point results in a thickening of the metastable crystals to construct more stable ones. Such a process was visualized by AFM equipped with a hot stage in monolayers of poly(ethylene oxide) lamellar crystals on a silicon wafer surface. Our observations show that the monolayers can be thickened in a stepwise manner during stepwise heating to temperatures below the melting point. Our analyses show the thickening process and mechanism as follows: At the first step a small portion of the lamellar crystals have the capability to be spontaneously thickened into a thicker one at a certain temperature range, giving rise to a difference in lamellar thickness. In the following step the thinner lamellae are forced to melt, and then the melted molecules enter an amorphous phase in which they are transported toward the thicker lamellae and finally recrystallize in the thicker ones. This inductive mechanism is analogous to the evaporation−condensation mechanism.