Dynamic mechanical relaxation of cross-linked styrene-butadiene polymers containing free chains: Possibility of reptation
Résumé
The structure of styrene-butadiene rubbers (SBRs) consists of chains attached to cross-links of relatively small number density. These rubbers show an α-relaxation process that is attributed to segmental motions of the attached chains. To investigate how an SBR's rubber-like behavior would change when free chains interpenetrate its structure, we prepared one SBR of mol wt 120 × 103containing 3-4% free chains of identical mol wt, and studied its dynamic mechanical relaxation. For 0.1 Hz frequency measurements, the α-relaxation peak appeared at 210 K, and a second relaxation peak, which we refer to as αR-relaxation, at 300 K. A third relaxation of small magnitude was resolved at temperatures between the αR- and the α-relaxation peaks, and its origin was discussed in relation to other studies. Spectral features of the αR-and the α-relaxations were found similar. We investigated the merits of the time-temperature superposition of the α- and of the αR-relaxations. The αRrelaxation vanished when the free chains were extracted from the SBR by swelling-extraction procedure. The features of α-relaxation can be interpreted as segmental motions of the SBR, but the features of the αR-relaxation is be interpretable only in terms of tube model for diffusion of free chains in a lightly cross-linked structure. We estimated the mol wt of these free chains and the mass between entanglements, and then used these quantities to calculate, by using the Doi-Edwards formalism, the relaxation time of the αR-process at 293 K. This relaxation time agrees with the experimental value. The αR-relaxation seems consistent with the tube model for diffusion of free chains in the cross-linked structure of SBR. © 2014 Elsevier Ltd. All rights reserved.
Mots clés
Butadiene
Chemical relaxation
Crosslinking
Dynamics
Elastomers
Relaxation time
Rubber
Styrene
Tubes (components)
Crosslinked structures
Dynamic mechanical relaxation
Experimental values
Extraction procedure
Frequency measurements
Relaxations
Styrene butadiene rubber
Time temperature superposition
Chains