材料
Online ISSN : 1880-7488
Print ISSN : 0514-5163
ISSN-L : 0514-5163
定常状態コンプライアンスの濃度依存性
栄永 義之倉田 道夫杉江 勉田村 幹雄
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1972 年 21 巻 224 号 p. 453-458

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The steady-state compliance Je as a function of the molecular weight M and the concentration c for polymer solution can be expressed as:
Je=αM/cRT for smaller values of c or M
M0/c2∼3 for larger values of c and M
Here α and β are constants and RT is used in its usual meaning. The second behavior of Je is characteristic of highly entangled system. In the concentration range where the transition from the first to the second behavior occurs, the Je displays the maximum.
Either of the two relaxation spectra, A and B, are found to be compatible with these observed behaviors of Je. These are:
(A) HW(τ)=1/2cRT/Mec/τ)1/2 0<τ<τc
HI(τ)=1/2(1-gN)cRT/Mec/τ)1/2 τc<τ<τ1
HB(τ)=1/hgNcRT/Me τl<τ<τm
τc1E-2, τmcE3.5, τlmeh(1/E-1)
(B) HW(τ)=1.75/3cRT/Mec/τ)2/3 0<τ<τc
HZ(τ)=1.75/3(1-gN)cRT/Mec/τ)2/3 τc<τ<τ1
HB(τ)=1/hgNcRT/Me τl<τ<τm
τc1E-1.5, τmcE3.5, τlme1.75h(1/E-1)/2
The former corresponds to the Rouse theory, while the latter to the Zimm theory. Here, τ1 represents the maximum relaxation time of the original Rouse or Zimm theory, Me is entanglement spacing, E is the number of entanglement point in a molecule, hence E=M/Me, and gN and h are parameters representing the intensities of HI and HB, respectively.
The viscosity η, storage modulus G' and loss modulus G" are also calculated on the basis of these spectra. These results are qualitatively in agreement with the observed one, particularly in the case of high value of h and low value of gN.

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