Origin of mechanical stress and rising internal energy during fast uniaxial extension of SBR melts. (25th August 2017)

• Record Type: Journal Article
• Authors: Lin, Panpan; Liu, Jianning; Zhao, Zhichen; Wang, Zhen-Gang; Wang, Shi-Qing
• Is Part Of: Polymer. Volume 124(2017)
• Page Start: 68
• Page End: 77
• Publication Date: 2017-08-25
• Subjects: Polymer melts -- Thermodynamics -- Uniaxial extension -- Melt rheology; Polymers -- Periodicals; Polymerization -- Periodicals; Polymères -- Périodiques; Polymérisation -- Périodiques; 547.7
• DOI: 10.1016/j.polymer.2017.07.041
• Languages: English
• ISSNs: 0032-3861

Abstract

Abstract: We carry out simultaneous mechanical and IR-thermal-imaging based temperature measurements of SBR melts during uniaxial extension in order to delineate the nature of the observed mechanical responses. Using the first law of thermodynamics, we evaluate the enthalpy change h 1 associated with the temperature rise in the extending melt, estimate the heat loss to the surrounding, and conclude that there is an appreciable non-thermal enthalpic buildup h 2 = ( w − h 1 − q ) during either adiabatic or isothermal extension. The monotonic increase of h 2 with the stretching ratio λ until the onset of inhomogeneous extension or melt rupture reveals that fast melt extension is largely elastic even after yielding in presence of partial chain disentanglement. At high rates, the lock-up of chain entanglement produces such a high level of h 2 that is rarely seen in extension of crosslinked rubbers. When melt extension is carried out under isothermal condition, we show that the time-temperature superposition principle (TTS) fails to predict the transient response of a SBR melt at a fixed effective rate involving three temperatures. The failure of the TTS suggests that the terminal chain dynamics show different temperature dependence from the local segmental dynamics that control the transient stress responses. Graphical abstract: Highlights: Melt stretching can store significant internal energy and cause conformational distortion at the bond level. Transient rheological response to startup extension does not follow the time-temperature superposition. Quenched melt stretched samples show retractive stress below Tg .