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Constraint-Limited Tube Orientation of Entangled Polymers in Oscillatory Shear Deformation
arXiv Physics
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이 매체는 공공·자유 라이선스로 본문을 직접 표시합니다.Condensed Matter > Soft Condensed Matter
[Submitted on 18 Jun 2026]
Title:Constraint-Limited Tube Orientation of Entangled Polymers in Oscillatory Shear Deformation
View PDF HTML (experimental)Abstract:We develop a molecularly motivated description of the nonlinear index (NLI) in oscillatory shear deformation of entangled polymers. The central assumption is that the shear component of the tube-orientation tensor cannot grow without bound. Convective constraint release (CCR), chain stretch, and tube dilation progressively reduce the number and lifetime of orientational constraints, but the maximum shear alignment of a tube segment is geometrically limited by $S_{xy}\leq 1/2$. This motivates a constraint-limited orientation closure in which the NLI first grows approximately with strain amplitude and then approaches the limiting value $\mathrm{NLI}_{\max}=3$ asymptotically rather than through an artificial cutoff. The same framework yields a molecular expression for the characteristic half-saturation strain $\gamma_s$, defined by $\mathrm{NLI}(\gamma_s)=3/2$, in terms of the entanglement number, oscillation frequency, and a critical number of remaining orientational constraints. We further derive architecture-dependent expressions for the nonlinear onset strain $\gamma_c$ for linear, sparsely long-chain-branched, and more regularly branched polymers. The resulting framework provides a compact bridge between Fourier harmonic analysis, CCR-based tube dynamics, and the progressive loss of orientational memory in highly deformed entangled polymer liquids.
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