A novel method for determining the melting behavior of ultrathin films

Experiments were performed on ultrathin (ca. 35 nm thick) Langmuir-Blodgett films of a double-bond-containing material (vinyl tetracosanoate). The melting/flow point of this deposited material, before and afterin situ polymerization by means of electron beams, was determined by using a Mettler FP5/52 hot stage in conjunction with a polarizing microscope. The melting/flow point observed in the deposited films was found to be higher than the bulk melting point as determined by the capillary method or differential scanning calorimetry. This apparent violation of the principle that a given substance's melting point becomes lower as the sample becomes thinner is explained in terms of the fact that the thin-film process observed is really a combination of two processes, initial melting and subsequent de-wetting, whereas the bulk process involves melting alone.