Dynamic modeling viscoelastic behavior

We have relied heavily on the use of models in discussing the viscoelastic behavior of polymers in the transient and dynamic experiments of the last few sections. The models were mechanical, however, and while they provide a way for understanding the phenomena involved, they do not explicitly relate these phenomena to molecular characteristics. To establish this connection is the objective of this section. 

Fig. 7 gives an example of such a comparison between a number of different polymer simulations and an experiment. The data contain a variety of Monte Carlo simulations employing different models, molecular dynamics simulations, as well as experimental results for polyethylene. Within the error bars this universal analysis of the diffusion constant is independent of the chemical species, be they simple computer models or real chemical materials. Thus, on this level, the simplified models are the most suitable models for investigating polymer materials. (For polymers with side branches or more complicated monomers, the situation is not that clear cut.) It also shows that the so-called entanglement length or entanglement molecular mass Mg is the universal scaling variable which allows one to compare different polymeric melts in order to interpret their viscoelastic behavior. 

The dynamic viscoelasticity of particulate gels of silicone gel and lightly doped poly-p-phenylene (PPP) particles has been studied under ac excitation [55]. The influence of the dielectric constant of the PPP particles has been investigated in detail. It is well known that the dielectric constant varies with the frequency of the applied field, the content of doping, or the measured temperature. In Fig. 11 is displayed the relationship between an increase in shear modulus induced by ac excitation of 0.4kV/mm and the dielectric constant of PPP particles, which was varied by changing the frequency of the applied field. AG increases with s2 and then reaches a constant value. Although the composite gel of PPP particles has dc conductivity, the viscoelastic behavior of the gel in an electric field is qualitatively explained by the model in Sect. 4.2.1, in which the effect of dc conductivity is neglected. 

The use of Cole-Cole plots is not very developed in practice, despite the fact that they open the way for the modeling of the viscoelastic behavior in dynamic as well as in static loading cases (through Laplace transform). By contrast, these plots could be interesting from the fundamental point of view if certain parameters would reveal a clear dependence with the crosslink density. The effects of crosslinking are difficult to detect on the usual viscoelastic properties, except for the variation of the rubbery modulus E0. 

On a global scale, the linear viscoelastic behavior of the polymer chains in the nanocomposites, as detected by conventional rheometry, is dramatically altered when the chains are tethered to the surface of the silicate or are in close proximity to the silicate layers as in intercalated nanocomposites. Some of these systems show close analogies to other intrinsically anisotropic materials such as block copolymers and smectic liquid crystalline polymers and provide model systems to understand the dynamics of polymer brushes. Finally, the polymer melt-brushes exhibit intriguing non-linear viscoelastic behavior, which shows strainhardening with a characteric critical strain amplitude that is only a function of the interlayer distance. These results provide complementary information to that obtained for solution brushes using the SFA, and are attributed to chain stretching associated with the space-filling requirements of a melt brush. 

Several researchers reported viscoelastic behavior of yeast suspensions. Labuza et al. [9] reported shear-thinning behavior of baker s yeast (S. cerevisiae) in the range of 1 to 100 reciprocal seconds at yeast concentrations above 10.5% (w/w). The power law model was successfully applied. More recently, Mancini and Moresi [10] also measured the rheological properties of baker s yeast using different rheometers in the concentration range of 25 to 200 g dm. While the Haake rotational viscometer confirmed Labuza s results on the pseudoplastic character of yeast suspension, the dynamic stress rheometer revealed definitive Newtonian behavior. This discrepancy was attributed to the lower sensitivity of Haake viscometer in the range of viscosity tested (1.5 to 12 mPa s). Speers et al. [11] used a controlled shear-rate rheometer with a cone-and-plate system to measure viscosity of... 

The linear viscoelastic behavior of the pure polymer and blends has already been described quantitatively by using models of molecular dynamics based on the reptation concept [12]. To describe the rheological behavior of the copolymers in this study, we have selected and extended the analytical approach of Be-nallal et al. [13], who describe the relaxation function G(t) of Hnear homopolymer melts as the sum of four independent relaxation processes [Eq. (1)]. Each term describes the relaxation domains extending from the lowest frequencies (Gc(t)) to the highest frequencies (Ghf( )), and is well defined for homopolymers in Ref [13]. 

These equations are often used in terms of complex variables such as the complex dynamic modulus, E = E + E", where E is called the storage modulus and is related to the amount of energy stored by the viscoelastic sample. E" is termed the loss modulus, which is a measure of the energy dissipated because of the internal friction of the polymer chains, commonly as heat due to the sinusoidal stress or strain applied to the material. The ratio between E lE" is called tan 5 and is a measure of the damping of the material. The Maxwell mechanical model provides a useful representation of the expected behavior of a polymer however, because of the large distribution of molecular weights in the polymer chains, it is necessary to combine several Maxwell elements in parallel to obtain a representation that better approximates the true polymer viscoelastic behavior. Thus, the combination of Maxwell elements in parallel at a fixed strain will produce a time-dependent stress that is the sum of all the elements ... 

In Chapter 3, we used the Rouse model for a polymer chain to study the diffusion motion and the time-correlation function of the end-to-end vector. The Rouse model was first developed to describe polymer viscoelastic behavior in a dilute solution. In spite of its original intention, the theory successfully interprets the viscoelastic behavior of the entanglement-free poljuner melt or blend-solution system. The Rouse theory, developed on the Gaussian chain model, effectively simplifies the complexity associated with the large number of intra-molecular degrees of freedom and describes the slow dynamic viscoelastic behavior — slower than the motion of a single Rouse segment. 

While the Choi and Schowalter [113] theory is fundamental in understanding the rheological behavior of Newtonian emulsions under steady-state flow, the Palierne equation [126], Eq. (2.23), and its numerous modifleations is the preferred model for the dynamic behavior of viscoelastic liquids under small oscillatory deformation. Thus, the linear viscoelastic behavior of such blends as PS with PMMA, PDMS with PEG, and PS with PEMA (poly(ethyl methacrylate))at <0.15 followed Palierne s equation [129]. From the single model parameter, R = R/vu, the extracted interfacial tension coefficient was in good agreement with the value measured directly. However, the theory (developed for dilute emulsions) fails at concentrations above the percolation limit, 0 > (p rc 0.19 0.09. 

As mentioned above, interfacial films exhibit non-Newtonian flow, which can be treated in the same manner as for dispersions and polymer solutions. The steady-state flow can be described using Bingham plastic models. The viscoelastic behavior can be treated using stress relaxation or strain relaxation (creep) models as well as dynamic (oscillatory) models. The Bingham-fluid model of interfacial rheological behavior (27) assumes the presence of a surface yield stress, cy, i.e.. 

The investigations of model compositions, based on linear elastomers and various fillers, have shown that the yield stress also may be characterized by the value of the complex shear modulus measured at various frequencies. The dependence of the dynamic modulus on the filler concentration characterizes critical concentrations of the filler, above which the viscoelastic behavior of composition drastically changes. Dynamic modulus corresponding to the yield stress does not depend on the matrix viscosity or its nature. This fact indicates a predominant role of the structural frame for rheological properties of filled polymers. 

Use of impact sled tests is the most common technique for determining the postcrash dynamic behavior of an aircraft occupant. The impact sled and target tracking facilities available at National Institute for Aviation Research (NIAR) were used to conduct a study on occupant responses in a crash environment. Parallel analysis capabilities, including a multibody dynamic model of the occupant and a finite element model of seat structures, have been developed. The analysis has been used to reasonably predict the Head Injury Criteria (HIC) as compart with the experimental impact sled tests for an occupant head impacting a panel. A nonlinear viscoelastic contact force model was shown to better predict the experimental data on the contact forces than the Hertzian models. Suitable values of the coefficients in the contact force model were obtained and the correlations between the coefficients, HIC, and maximum deformation of the front panel were determined. A non-sled test method of pendulum-type has been designed to determine the head injuries as well as the performance of each particular impact absorber. 

Of course, in order to describe properly the behavior of a polymer, one would need to have the expression of G( ) and its dependence on the material characteristics, which means modeling the system and drawing a physically plausible correlation between its nano- or microscale properties and its macroscopic response. A brilliant example is the well-known model of viscoelasticity due to J. C. Maxwell, " which has been used for longer than a century by several generations of physicists and engineers. Nowadays, Maxwell s picture is still very popular and it is often deployed to describe the dynamics of viscoelastic materials during nanofabrication processes. For... 

DPD simulation has been applied to predict the rheological and viscoelastic behaviors of nanopartide-polymer nanocomposites and to examine the effects of particle shape, particle-particle interaction, and partide dispersion states of such behaviors. It was found that partide-particle interaction has a distinct effect on the dynamic shear modulus. Havet and Isayev [39,40] proposed a rheological model to predict the dependence of dynamic properties of highly interactive filler-polymer mixtures on strain and the dependence of shear stress on shear rate. 

---