Temperature dependence on free volume in cured natural rubber and styrene-butadiene rubber blends

A systematic study on the evolution of free volume as a function of the temperature in vulcanized at 433 K natural rubber (NR) and styrene butadiene rubber (SBR) in 25-75, 50-50, 75-25 NR-SBR (percent content of pure NR and SBR, respectively) blends was studied by positron annihilation lifetime spectroscopy. All samples were prepared with sulfur and TBBS (n-t-butyl-2-benzothiazole sulfenamide) as accelerator. The glass transition temperatures of the samples studied were determined by differential scanning calorimetry (DSC) and from lifetime data. In general, a sigmoidal-like complex behavior of the long-lived lifetime component, linked to the nanohole free volume, as a function of the temperature was found. For SBR, the slope of the ortho-positronium lifetime against temperature curves could be well-fitted using a linear function. For blends and also for NR, two different linear functions were necessary. This last behavior is explained in terms of the supercooled process involving a reconfiguration of the elastomeric chains. In the case of blends, the state of cure of NR and SBR in each NR-SBR sample was also taken into account in the discussion of the results obtained. Besides, thermal expansion coefficients of the free volumes in the transition and glassy region of all compounds were estimated. The differences observed in the values of this parameter are discussed by taking into account the morphology and formulation of each blend, the crosslink densities, and the role of the interphases formed between both NR and SBR elastomers.