Dynamic mechanical measurements Payne effect

Filler-filler interaction (Payne effect) - The introduction of reinforcing fillers into rubbery matrices strongly modifies the viscoelastic behavior of the materials. In dynamic mechanical measurements, with increasing strain amplitude, reinforced samples display a decrease of the storage shear modulus G. This phenomenon is commonly known as the Payne effect and is due to progressive destruction of the filler-filler interaction [46, 47]. The AG values calculated from the difference in the G values measured at 0.56% strain and at 100% strain in the unvulcanized state are used to quantify the Payne effect. 

Non-linear mechanical properties were observed for rubber eomposites and referred to as the Payne effect. The Payne effeet was interpreted as due to filler agglomeration where the filler clusters formed eontained adsorbed rubber. The occluded rubber molecules within filler elusters eould not eontribute to overall elastic properties. The composites behaved similarly to rubber composites with higher filler loading. Uniform and stable filler dispersion is required for rubber composites to exhibit linear viscoelastic behaviour. Payne performed dielectric measurements on SBR vulcanizates containing silica or carbon black. The dielectric data were used to construct time-temperature superposition master curves. The reference temperature increased with crosslinking but not significantly with filler. Comparison of dynamic mechanical and dielectric results for the SBR blended with NR was made and interpreted. ... 

Non-linear viscoelastic properties were observed for fumed silica-poly(vinyl acetate) (PVAc) composites, with varying PVAc molar mass and including a PVAc copolymer with vinyl alcohol. Dynamic mechanical moduli were measured at low strains and found to decrease with strain depending on surface treatment of the silica. The loss modulus decreased significantly with filler surface treatment and more so with lower molar mass polymer. Copolymers with vinyl alcohol presumably increased interactions with silica and decreased non-linearity. Percolation network formation or agglomeration by silica were less important than silica-polymer interactions. Silica-polymer interactions were proposed to form trapped entanglements. The reinforcement and nonlinear viscoelastic characteristics of PVAc and its vinyl alcohol copolymer were similar to observations of the Payne effect in filled elastomers, characteristic of conformations and constraints of macromolecules. ... 

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