Computational Materials Science of Polymers

Appendix 6: On Formation of Super-Molecular Structures in Amorphous Polymers

1 Scheme of Formation of the Super-Molecular Structure

The experimental data obtained up to the present time, as well as theoretical investigations of polymers enable us to appoint a scheme of the formation of super-molecular structures and, yielding from this scheme, to make an attempt in future to set a connection between the chemical structure of a polymer, its super-molecular structure and physical properties [236]. The question about super-molecular structures and their forms was originally formulated in ref. [237]. Further on, various models of super-molecular structure appeared [238, 239], which allow an explanation of a series of properties of amorphous polymers in solution, melt and solid state. Simultaneously with model ideas, numerous experiments with obtaining super-molecular structure by various methods were performed, with the method of electron microscopy being the chief method. The most typical situation in amorphous polymers observed is the picture of globules the sizes of which correspond to aggregates of tens and hundreds of macromolecules.

Let us dwell on problems of super-molecular structure formation and description of this process with the help of an analytical apparatus, developed in refs. [240 242]. Before passing to the essence of the problem, let us note in brief the main results of these works, which will be necessary for us for future discussion. Suggested by Lifshitz in ref. [240] was the equation:

(A-6-1)
(A-6-2)

where ? is the integral operator; ? ? = ?g( x - x') ?( x') d 3 x'; g( x...

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