Korea-Australia Rheology Journal, Vol.16, No.2, 91-99, June, 2004
Conformational changes of short, discrete Rouse chain during creep and recovery processes
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For the Rouse chain composed of infinite number of beads (continuous limit), conformational changes during the creep and creep recovery processes was recently analyzed to reveal the interplay among all Rouse eigenmodes under the constant stress condition (Watanabe and Inoue, Rheol. Acta, 2004). For completeness of the analysis of the Rouse model, this paper analyzes the conformational changes of the discrete Rouse chain having a finite number of beads (N = 3 and 4). The analysis demonstrates that the chain of finite N exhibits the affine deformation on imposition/removal of the stress and this deformation gives the instantaneous component of the recoverable compliance, JR(0) = 1/(N-1)νkBT with ν and kB being the chain number density and Boltzmann constant, respectively. (This component vanishes for N → ∞.) For N = 2, it is known that the chain has only one internal eigenmode so that the affinely deformed conformation at the onset of the creep process does not change with time t and JR(t) coincides with JR(0) at any t (no transient increase of JR(t)). However, for N ≥ 3, the chain has N-1 eigenmodes (N-1 ≥ 2), and this coincidence vanishes. For this case, the chain conformation changes with t to the non-affine conformation under steady flow, and this change is governed by the interplay of the Rouse eigenmodes (under the constant stress condition). This conformational change gives the non-instantaneous increase of JR(t) with t, as also noted in the continuous limit (N → ∞).
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