Delayed Arm Retraction Controls the Nonlinear Oscillatory Response of Long-Chain-Branched Polymer Melts

Abstract

Long-chain branching profoundly modifies the nonlinear oscillatory response of entangled polymer melts by introducing arm-retraction pathways absent in linear polymers. We present a molecular tube theory that explains the characteristic maximum of the Nonlinearity Index (NLI) observed experimentally in long-chain-branched polymers. The theory extends the recently developed nonlinear tube-orientation description of linear polymers by incorporating branch-point force transmission and delayed arm retraction. The backbone initially develops nonlinear orientation as in the corresponding linear polymer, whereas long-arm retraction subsequently relaxes the stored branch-point tension and progressively erases backbone orientational memory. This competition produces a characteristic NLI maximum followed by a post-peak decay. The theory predicts two distinct nonlinear regimes corresponding to sparse and dense long-chain branching and introduces an architecture parameter governing the height and width of the nonlinear peak. The resulting framework provides a molecular interpretation of nonlinear Fourier rheology and directly links the nonlinear harmonic response to polymer architecture.