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Polymer conformation at the polymer melt surface
Author(s) -
Silberberg A.
Publication year - 1989
Publication title -
makromolekulare chemie. macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 0258-0322
DOI - 10.1002/masy.19890230103
Subject(s) - polymer , surface (topology) , surface tension , chain (unit) , amorphous solid , lamella (surface anatomy) , materials science , crystallography , chemical physics , geometry , physics , chemistry , mathematics , composite material , thermodynamics , astronomy
Due to the symmetry which characterizes the surroundings of each chain segment in the amorphous melt all (but end) segments are equivalent in their embedment in space. Energetic interactions between segments are confined to segments in contact. Hence, in the presence of a surface only the segments actually in the surface layer will be affected and will have a statistical weight and Boltzmann factor different from segments in the bulk. The number of segments so involved is fixed, since the extent of the surface is controlled. The partition function is comprised of factors which depend neither upon the order of the segments in the chain nor upon the conformation of any particular chain. Only segments finding themselves in the surface contribute to the surface tension, with the largest contribution deriving from the density transition in the interface. This, at most temperatures, is confined to a lamella one segment layer, or less, thick. For polymer of high enough molecular weight end‐effects can be neglected and no allowance for the presence of ends is made here. It is then possible to reach a representation of surface tension in reduced coordinates, as shown already by Posner and Sanchez. Changes in chain conformation near the surface are calculated.