Effect of grafted alumina nanoparticles on thermal and dynamic mechanical properties of the styrene-butadiene rubber

Elastomers filled with hard nanoparticles are of great technical importance for the rubber industry. In general, fillers improve mechanical properties of polymer materials, e.g. elastic moduli, tensile strength etc. The smaller the size of the particles the larger is the interface where interactions between polymer molecules and fillers can generate new properties. The aim of this contribution is to study the influence of the fillers’ surface treatment on the thermal and mechanical behavior of nanocomposites made of styrene-butadiene rubber (SBR). Three types of nanocomposites are investigated : (i) SBR-unmodified alumina, (ii) SBR – silanized alumina and (iii) SBR – alumina grafted to polymer chains. The surface-modified alumina nanoparticles were prepared using the method described in [1]. The grafting of the SBR chains to the alumina nanoparticles was realized by means of the procedures described in [2] and [3].
Temperature Modulated Differential Scanning Calorimetry (TMDSC) and Dynamic Mechanical Analysis (DMA) are well appropriated tools to investigate the thermal and dynamic glass transition behavior of the different nanocomposites, which is expected to be very sensitive to interfacial interactions between the nanoparticles and matrix molecules. TMDSC experiments reveal that all of the nanocomposites undergo a single glass transition. Thus, interphases induced by interfacial interactions do not manifest themselves by an additional glass transition unless it is hidden by the one of the matrix. Moreover, TMDSC measurements reveal that in general the glass transition temperature Tg depends in a complex manner on the concentration and surface treatment of the nanoparticles. The most important change of Tg is observed for the grafted nanocomposites: increasing the nanoparticle weight concentration beyond 4% yields an increase of Tg by 4 K. The corresponding slowing down of the molecular dynamics goes along with a significant decrease of the relaxator strength. More generally the presented results prove that, at the same filler concentration, the number of degrees of freedom freezing at the glass transition in case of un-grafted systems is practically independent on the chemical nature of the particles surface whereas it changes when there exist covalent bonds between the polymer molecules and the nanoparticles.
DMA was used to probe the rheological behaviour of the nanocomposites under oscillatory shear. Isothermal frequency sweeps performed at different temperatures yield the real (G’) and imaginary (G”) parts of the complex shear modulus. Linear response regime conditions were strictly respected. The temperature-frequency equivalence principle was exploited to construct mastercurves for G’ and G” at the reference temperature T=273 K. As usual in polymers, three different behaviors were observed: the dynamic glass transition at high frequencies, the entanglement plateau at intermediary frequencies and viscoelastic “flowing” at very low frequencies. It generally appears that the filling of the SBR matrix with nanoparticles leads to an increase of the storage modulus that is more prominent in the rubbery region than in the glassy segment. While, in the low frequency regime, untreated and silanized alumina yield a mechanical behaviour that is rather near to the one of the neat SBR matrix, the grafting of elastomer molecules to the silanized fillers obviously induces a quasi-solid like response of the system.

References:
1. Y.-Ch. Yang, S.-B. Jeong, B.-G. Kim, P.-R. Yoon, Powder Technology, 191, 117–121, 2009.
2. E. Passaglia, F. Donati, Polymer, 48, 35-42, 2007.
3. A. Bhattacharya, B. Misra, Prog. Polym. Sci. 29, 767–814, 2004.