Relaxation Behavior and Time-Temperature Superposition (TTS) Profiles of Thermally Aged Styrene-Butadiene Rubber (SBR)

Kewei Xiang; Siduo Wu; Guangsu Huang; Jing Zheng; Jingyun Huang; Guangxian Li

Macromolecular Research, Vol.22, No.8, 820-825, August, 2014

DOI10.1007/s13233-014-2106-x Export Citation

Relaxation Behavior and Time-Temperature Superposition (TTS) Profiles of Thermally Aged Styrene-Butadiene Rubber (SBR)

Kewei Xiang, Siduo Wu, Guangsu Huang^†, Jing Zheng, Jingyun Huang, and Guangxian Li^†

State Key Laboratory of Polymer Material Engineering, College of Polymer Science and Engineering, Sichuan University, Chengdu, 610065, P. R. China, Korea

E-mail:,

In this work, styrene-butadiene rubber (SBR) was thermally aged at 130 ℃ with ageing period up to 4 days. The relaxation behavior was studied by dynamic mechanical analysis (DMA) in temperature scanning mode at multifrequencies and the crosslinking network was characterized by swelling method. Glass transition temperature (Tg) and activation energies (Ea) during transition evaluated by Starkweather method were found to increase after ageing. Time-temperature superposition (TTS) procedure was performed to obtain master curve and shift factors (αT). The derived αTs were fitted by William-Landel-Ferry (WLF) and Vogel-Fulcher-Tamman (VFT) equations. WLF fitting parameters confirmed decreased free volume fraction (f ) and thermal expansion coefficient (αf) near Tg versus ageing time. Temperature dependent relaxation properties were examined by VFT fitting parameter D. It was found that the aged SBR displayed more brittle behavior, becoming more and more deviated from Arrhenius fashion. This phenomenon was illustrated by the enhanced intermolecular coupling and severe crosslinking during ageing.

Keywords:styrene-butadiene rubber;thermal ageing;relaxation properties.

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[2] Li MC, Ge X, Cho UR, Macromol. Res., 21(7), 793 (2013)

[3] Seo B, Kim H, Paik HJ, Kwag GH, Kim W, Macromol. Res., 21(7), 738 (2013)

[4] Mele P, Angellier-Coussy H, Molina-Boisseau S, Dufresne A, Biomacromolecules, 12(5), 1487 (2011)

[5] Kumar ES, Das CK, Banik K, Menning G, Compos. Sci. Technol., 67, 1202 (2007)

[6] Musto P, Ragosta G, Abbate M, Scarinzi G, Macromolecules, 41(15), 5729 (2008)

[7] Kwak SY, Ahn DU, Choi J, Song HJ, Lee SH, Polymer, 45(20), 6889 (2004)

[8] Zhu ZY, Thompson T, Wang SQ, Meerwall EDV, Halasa A, Macromolecules, 31, 8816 (2005)

[9] Patel M, Polym. Test., 23, 107 (2004)

[10] Shivakumar E, Das CK, Segal E, Narkis M, Polymer, 16, 3363 (2005)

[11] Jouault N, Vallat P, Dalmas F, Said S, Jestin J, Boue F, Macromolecules, 42(6), 2031 (2009)

[12] Xiang K, Wang X, Huang G, Zheng J, Huang J, Li G, Polym. Degrad. Stab., 97, 1704 (2012)

[13] Mark JE, Rubb. Chem. Technol., 55, 762 (1982)

[14] Ovejero G, Perez P, Romero MD, Guzman I, Diez E, Eur. Polym. J., 43, 1444 (2007)

[15] Van Krevelen DW, Properties of Polymers: Their Estimation and Correlation With Chemical Structure, Elsevier, Amsterdam (1976)

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[17] Starkweather HWJ, Macromolecules, 21, 1798 (1988)

[18] Roland CM, Macromolecules, 27(15), 4242 (1994)

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[20] Ngai KL, Roland CM, Macromolecules, 27(9), 2454 (1994)

[21] Ferry JD, Viscoelastic Properties of Polymers, J. Wiley, New York (1980)

[22] Williams ML, Landell RF, Ferry JD, J. Am. Chem. Soc., 77, 3701 (1955)

[23] Qin Q, McKenna B, J. Non-Cryst. Solids, 352, 2977 (2006)

[24] Kuwahara H, Sudo S, Iijima M, Ohya S, Polym. Dgrad. Stab., 95, 2461 (2010)