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First-harmonic intrinsic nonlinearity of model polymer solutions in medium amplitude oscillatory shear (MAOS)

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Abstract

First-harmonic MAOS moduli were demonstrated experimentally using monodisperse linear polystyrene (PS) solutions at different concentrations. Two first-harmonic intrinsic nonlinearities are asymptotic deviations from two linear viscoelastic moduli and obtained in medium amplitude oscillatory shear (MAOS) regime. Master curves of first-harmonic MAOS moduli for PS solutions provided novel information which has never been reported before. The interrelationship between first-harmonic and third-harmonic MAOS moduli was evaluated at low and high De. At the low-De limit, all solutions followed the universal interrelation predicted by fourth-order fluid expansion. At the high-De limit, where no universal interrelation exists, the average first-harmonic to third-harmonic elastic MAOS moduli ratio was −22.26, and for viscous counterparts, the magnitude and sign of this ratio changed on increasing frequency. Unentangled and entangled solutions were distinguished using normalized viscous moduli at De > 1. Viscous MAOS moduli normalized by SAOS complex modulus displayed a plateau for unentangled solutions and a decreasing behavior for entangled solutions. First-harmonic MAOS moduli of entangled solutions agreed well with multimode molecular stress function (MSF) predictions under the all relaxation mode assumption, which contrasted with third-harmonic MAOS predictions using the terminal relaxation mode assumption. It is expected that the first-harmonic MAOS results in this paper will be good reference information for future MAOS studies and computer simulations.

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  1. School of Chemical and Biomolecular Engineering, Pusan National University, Busan, 46241, Republic of Korea

    Hyeong Yong Song & Kyu Hyun

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  1. Hyeong Yong Song
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  2. Kyu Hyun
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Correspondence to Kyu Hyun.

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Song, H.Y., Hyun, K. First-harmonic intrinsic nonlinearity of model polymer solutions in medium amplitude oscillatory shear (MAOS). Korea-Aust. Rheol. J. 31, 1–13 (2019). https://doi.org/10.1007/s13367-019-0001-x

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  • DOI: https://doi.org/10.1007/s13367-019-0001-x

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