Thermorheological complexity results

Many amorphous homopolymers and random copolymers show thermorheologically simple behavior within the usual experimental accuracy. Plazek (23,24), however, found that the steady-state viscosity and steady-state compliance of polystyrene cannot be described by the same WLF equation. The effect of temperature on entanglement couplings can also result in thermorheologically complex behavior. This has been shown on certain polymethacrylate polymers and their solutions (22, 23, 26, 31). The time-temperature superposition of thermorheologically simple materials is clearly not applicable to polymers with multiple transitions. The classical study in this area is that by Ferry and co-workers (5, 8) on polymethacrylates with relatively long side chains. In these the complex compliance is the sum of two contributions with different sets of relaxation mechanisms the compliance of the chain backbone and that of the side chains, respectively. 

In the first experiments over an extended frequency range, the biaxial viscoelastic as well as uniaxial viscoelastic properties of wet cortical human and bovine femoral bone were measured using both dynamic and stress relaxation techniques over eight decades of frequency (time) [Lakes et al, 1979]. The results of these experiments showed that bone was both nonlinear and thermorheologically complex, that is, time-temperature superposition could not be used to extend the range of viscoelastic measurements. A nonlinear constitutive equation was developed based on these measurements [Lakes and Katz, 1979a]. 

From the experimental results obtained, it was concluded that the synthetic hinders were thermorheologically complex materials as a consequence of the formation of a multiphase system. In fact, their mechanical behaviour is different according to the range of temperatures studied. While at low temperatures the binder mimics the mechanical properties of the oil-resin phase, at high temperatures the mechanical behaviour of the binder seems to be due to the polymer. Finally, the complex viscosity of these blends can be predicted using a logarithmic mixing rule, as will be discussed later. 

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