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. 

Fig. 2-24 Maxwell model used to explain viscoelastic behavior.

The Maxwell model is also called Maxwell fluid model. Briefly it is a mechanical model for simple linear viscoelastic behavior that consists of a spring of Young s modulus (E) in series with a dashpot of coefficient of viscosity (ji). It is an isostress model (with stress 5), the strain (f) being the sum of the individual strains in the spring and dashpot. This leads to a differential representation of linear viscoelasticity as d /dt = (l/E)d5/dt + (5/Jl)-This model is useful for the representation of stress relaxation and creep with Newtonian flow analysis. 

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. 

Contents Chain Configuration in Amorphous Polymer Systems. Material Properties of Viscoelastic Liquids. Molecular Models in Polymer Rheology. Experimental Results on Linear Viscoelastic Behavior. Molecular Entan-lement Theories of Linear iscoelastic Behavior. Entanglement in Cross-linked Systems. Non-linear Viscoelastic-Properties. 

Real polymers are more complex than these simple mechanical models. Qualitatively, when a real polymer is forced to flow through a contraction or expansion in an extrusion screw, it will exhibit viscoelastic behaviour. The polymer molecules will be elongated if forced through a contraction, or they will retract when they flow into an expansion. The effect of viscoelastic behavior in a capillary rheometer is observed in the form of recirculation flow just before the polymer enters the... 

In order to understand the effects of filler loading and filler-filler interaction strength on the viscoelastic behavior, Chabert et al. [25] proposed two micromechanical models (a self-consistent scheme and a discrete model) to account for the short-range interactions between fillers, which led to a good agreement with the experimental results. The effect of the filler-filler interactions on the viscoelasticity... 

The bead-spring models are devices to circumvent the complications of the local motion problem and still obtain information on the large-scale configurational relaxations which control viscoelastic behavior. Their utility lies in the... 

Accordingly, given the necessity from equilibrium coil dimensions that bt> 1, the shear rate and frequency departures predicted by FENE dumbbells are displaced from each other. Moreover, the displacement increases with chain length. This is a clearly inconsistent with experimental behavior at all levels of concentration, including infinite dilution. Thus, finite extensibility must fail as a general model for the onset of nonlinear viscoelastic behavior in flexible polymer systems. It could, of course, become important in some situations, such as in elongational and shear flows at very high rates of deformation. 

The combination of spring and dashpot in series is called the Maxwell model, and was in fact first investigated by the same Maxwell famous for his work on gases and molecular statistics. It is used to model the viscoelastic behavior of uncross-linked polymers. The spring is used to describe the recoverability of the chains that are elongated, and the dashpot the permanent deformation or creep (resulting from the uncross-linked chains irreversibly sliding by one another). 

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. 

Differential Viscoelastic Models. Differential models have traditionally been the choice for describing the viscoelastic behavior of polymers when simulating complex flow systems. Many differential viscoelastic models can be described by the general form... 

Integral viscoelastic models. Integral models with a memory function have been widely used to describe the viscoelastic behavior of polymers and to interpret their rheological measurements [37, 41, 43], In general one can write the single integral model as... 

There are several models to describe the viscoelastic behavior of different materials. Maxwell model, Kelvin-Voigt model, Standard Linear Solid model and Generalized Maxwell models are the most frequently applied. 

Models of mechanical behavior of tissues have been difficult to develop primarily because of the time dependence of the viscoelasticity. Analysis of viscoelastic behavior of even simple polymers at strains greater than a few percent is not accurate. In addition, most tissues undergo strains larger than a few percent, which makes the analysis require an understanding of the elongation behavior. In this chapter we focus on using modeling techniques to analyze the physical basis for determination of the tensile behavior of ECMs found in connective tissue. 

Another approach that has physical merit is to model the behavior of viscoelastic materials as a series of springs (elastic elements) and dashpots (viscous elements) either in series or parallel (see Figure 8.1). If the spring and dashpot are in series, which is described as a Maxwell mechanical element, the stress in the element is constant and independent of the time and the strain increases with time. 

Figure 8.1. Diagram showing Maxwell mechanical model of viscoelastic behavior of connective tissues. In this model an elastic element (spring) with a stiffness Em is in series with a viscous element (dashpot) with viscosity T m. This model is used to represent time dependent relaxation of stress in a specimen bold of fixed length.

In the simplest case the stress required to strain a viscoelastic material to a particular strain is the sum of an elastic term and a viscous term. This is somewhat more complicated for most tissues but this thought process can be used to understand the behavior of tendon after the crimp is straightened. Below we use this approach to model the behavior of tendon. 

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