結晶性高分子の緩和分布 : 結晶性高分子の構造とレオロジー

概要

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The relaxation time spectrum of the so-called Rouse chain is examined from the viewpoint of statistical thermodynamics of irreversible processes, and two ways of approach to explain the flat shape of the spectrum obtained for crystalline polymers, one way is to modify the elastic character of the original Rouse chain and the other is to modify the internal frictional character, are indicated to be equivalent. The former way of approach seems to be more comprehensible than the latter, because the latter way in general inevitably introduces multiple activation energies and this makes the Ferry's reduction rule invalid, while recent experimental results for crystalline polymers demonstrate the validity of this rule. As the well-known -1/2 slope of the wedge-shaped part of the spectrum for amorphous polymers is in the former way of approrch shown to be connected with one dimensional distribution of normal modes in the chain taken for an elastic body, so the flat shape of the spectrum for crystalline polymers would correspond to some relaxation mechanism where more-than-one dimensional distribution of normal modes play a role. Taking account of the anisotropy for the intersubmolecular elastic force owing to the presence of crystalline regions, we can obtain a nearly flat shape of the spectrum in the range of large relaxation time under suitable conditions.
社団法人日本材料学会の論文
1959-04-15