Abstract

In the constitutive equation modeling of a (linear) viscoelastic material, the “fading memory” of the relaxation modulus G(t) is a fundamental concept that dates back to Boltzmann [Ann. Phys. Chem. 7, 624 (1876)]. There have been various proposals that range from the experimental and pragmatic to the theoretical about how fading memory should be defined. However, if, as is common in the rheological literature, one assumes that G(t) has the following relaxation spectrum representation: G(t)=∫0∞ exp(−t/τ)[H(τ)/τ]dτ, t > 0, then it follows automatically that G(t) is a completely monotone function. Such functions have quite deep mathematical properties, that, in a rheological context, spawn interesting and novel implications. For example, because the set of completely monotone functions is closed under positive linear combinations and products, it follows that the dynamics of a linear viscoelastic material, under appropriate stress–strain stimuli, will involve a simultaneous mixture of different molecular interactions. In fact, it has been established experimentally, for both binary and polydisperse polymeric systems, that the dynamics can simultaneously involve a number of different molecular interactions such as the Rouse, double reptation and/or diffusion, [W. Thimm et al., J. Rheol., 44, 429 (2000); F. Leonardi et al., J. Rheol. 44, 675 (2000)]. The properties of completely monotone functions either yield new insight into modeling of the dynamics of real polymers, or they call into question some of the key assumptions on which the current modeling is based, such as the linearity of the Boltzmann model of viscoelasticity and/or the relaxation spectrum representation for the relaxation modulus G(t). If the validity of the relaxation spectrum representation is accepted, the resulting mathematical properties that follow from the complete monotonicity of G(t) allows one to place the classical relaxation model of Doi and Edwards [M. Doi and S. F. Edwards, J. Chem. Soc., Faraday Trans. 2 74, 1789 (1978)], as a linear combination of exp(−t/τ*) relaxation processes, each with a characteristic relaxation time τ*, on a more general and rigorous footing.

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