Microscopic Nonaffine Deformation Theory of LAOS in Polymers

Fuente: arXiv
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Autores principales: Nichetti, Dario, Zaccone, Alessio
Formato: Preprint
Publicado: 2026
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author Nichetti, Dario
Zaccone, Alessio
author_facet Nichetti, Dario
Zaccone, Alessio
contents We develop a molecularly motivated framework connecting large-amplitude oscillatory shear (LAOS) nonlinearities in entangled polymers to frequency-dependent nonaffine relaxation in disordered solids. The central idea is that the first harmonic in LAOS measures the residual phase-locked elastic response, whereas the higher harmonics encode the Fourier signature of strain-dependent nonaffine relaxation. The finite-amplitude modulus is interpreted as a local tangent stiffness of the evolving microstructure, in the spirit of elastoplastic and incremental nonaffine models. For entangled polymers, the analogue of the decreasing coordination number in cage-breaking theories of glass mechanics is identified not with the tube-orientation tensor itself, but with the fraction of surviving tube constraints. This distinction leads naturally to a crossover description controlled by a characteristic strain amplitude $γ_c$, rather than by universal fixed power-law exponents. The fitted value $N_{\max}\simeq1.72$ indicates that the present experimental data approach a strong but not fully saturated nonlinear state, remaining below the ideal limiting value predicted for complete constraint collapse. Finally, a constraint-counting argument combining an eight-chain affine network representation with the central-force nonaffine isostatic threshold gives a limiting estimate $|\mathrm{NLI}|_{\max}=3$. The results support the interpretation of the NLI as a Fourier-resolved dynamic nonaffinity parameter and establish a bridge between tube-based polymer dynamics, LAOS harmonic analysis, elastoplastic rheology, and microscopic nonaffine lattice dynamics.
format Preprint
id arxiv_https___arxiv_org_abs_2605_21021
institution arXiv
publishDate 2026
record_format arxiv
spellingShingle Microscopic Nonaffine Deformation Theory of LAOS in Polymers
Nichetti, Dario
Zaccone, Alessio
Soft Condensed Matter
Disordered Systems and Neural Networks
Statistical Mechanics
Chemical Physics
We develop a molecularly motivated framework connecting large-amplitude oscillatory shear (LAOS) nonlinearities in entangled polymers to frequency-dependent nonaffine relaxation in disordered solids. The central idea is that the first harmonic in LAOS measures the residual phase-locked elastic response, whereas the higher harmonics encode the Fourier signature of strain-dependent nonaffine relaxation. The finite-amplitude modulus is interpreted as a local tangent stiffness of the evolving microstructure, in the spirit of elastoplastic and incremental nonaffine models. For entangled polymers, the analogue of the decreasing coordination number in cage-breaking theories of glass mechanics is identified not with the tube-orientation tensor itself, but with the fraction of surviving tube constraints. This distinction leads naturally to a crossover description controlled by a characteristic strain amplitude $γ_c$, rather than by universal fixed power-law exponents. The fitted value $N_{\max}\simeq1.72$ indicates that the present experimental data approach a strong but not fully saturated nonlinear state, remaining below the ideal limiting value predicted for complete constraint collapse. Finally, a constraint-counting argument combining an eight-chain affine network representation with the central-force nonaffine isostatic threshold gives a limiting estimate $|\mathrm{NLI}|_{\max}=3$. The results support the interpretation of the NLI as a Fourier-resolved dynamic nonaffinity parameter and establish a bridge between tube-based polymer dynamics, LAOS harmonic analysis, elastoplastic rheology, and microscopic nonaffine lattice dynamics.
title Microscopic Nonaffine Deformation Theory of LAOS in Polymers
topic Soft Condensed Matter
Disordered Systems and Neural Networks
Statistical Mechanics
Chemical Physics
url https://arxiv.org/abs/2605.21021