Crystal transition behavior of lignoceric acid (LA) monolayer was structurally investigated by electron diffraction (ED) in conjunction with scanning force microscopy (SFM). LA molecules form two-dimensional hexagonal crystallites right after one spreads a solution at the air/water interface. The hexagonal-rectangular transition of the LA monolayer was attained by two different experimental procedures: monolayer compression under an isothermal condition and monolayer cooling under an isobaric condition. In the compression process, the hexagonal and rectangular phases coexisted in the monolayer at the surface pressure, π, of 10 mN m-1, which was slightly lower than the plateau pressure, and the subphase temperature of 293 K. When the π exceeded the plateau pressure, the hexagonal phase in the LA monolayer was entirely transformed to the rectangular one. High-resolution SFM showed that the crystal transition from the hexagonal to rectangular phase proceeded via a quasi-disordered phase upon compression. A similar hexagonal-rectangular transition was also observed during the monolayer cooling process at the π of 15 mN m-1. Based on SFM observation, we claimed that the molecular ordering or packing state in the rectangular lattice induced by cooling was better than that by the monolayer compression. Finally, the crystal transition mechanisms for these two procedures were proposed.
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