Viscoelasticity—Maxwell Model

The Maxwell class of viscoelastic constitutive equations are described by a simpler form of Equation (1.22) in which A = 0. For example, the upper-convected Maxwell model (UCM) is expressed as... 

The grade of polypropylene whose creep curves are given in Fig. 2.5 is to have its viscoelastic behaviour fltted to a Maxwell model for stresses up to 6 MN/m and times up to ICKX) seconds. Determine the two constants for the model and use these to determine the stress in the material after 900 seconds if the material is subjected to a constant strain of 0.4% throughout the 900 seconds. 

Creep modeling A stress-strain diagram is a significant source of data for a material. In metals, for example, most of the needed data for mechanical property considerations are obtained from a stress-strain diagram. In plastic, however, the viscoelasticity causes an initial deformation at a specific load and temperature and is followed by a continuous increase in strain under identical test conditions until the product is either dimensionally out of tolerance or fails in rupture as a result of excessive deformation. This type of an occurrence can be explained with the aid of the Maxwell model shown in Fig. 2-24. 

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. 

It is likely that most biomaterials possess non-linear elastic properties. However, in the absence of detailed measurements of the relevant properties it is not necessary to resort to complicated non-linear theories of viscoelasticity. A simple dashpot-and-spring Maxwell model of viscoelasticity will provide a good basis to consider the main features of the behaviour of the soft-solid walls of most biomaterials in the flow field of a typical bioprocess equipment. 

One feature of the Maxwell model is that it allows the complete relaxation of any applied strain, i.e. we do not observe any energy stored in the sample, and all the energy stored in the springs is dissipated in flow. Such a material is termed a viscoelastic fluid or viscoelastic liquid. However, it is feasible for a material to show an apparent yield stress at low shear rates or stresses (Section 6.2). We can think of this as an elastic response at low stresses or strains regardless of the application time (over all practical timescales). We can only obtain such a response by removing one of the dashpots from the viscoelastic model in Figure 4.8. When a... 

This material is a linear viscoelastic solid and is described by the multiple Maxwell model with an additional term, the spring elasticity... 

We have developed the idea that we can describe linear viscoelastic materials by a sum of Maxwell models. These models are the most appropriate for describing the response of a body to an applied strain. The same ideas apply to a sum of Kelvin models, which are more appropriately applied to stress controlled experiments. A combination of these models enables us to predict the results of different experiments. If we were able to predict the form of the model from the chemical constituents of the system we could predict all the viscoelastic responses in shear. We know that when a strain is applied to a viscoelastic material the molecules and particles that form the system gradual diffuse to relax the applied strain. For example, consider a solution of polymer... 

For a viscoelastic solid the situation is more complex because the solid component will never flow. As the strain is applied with time the stress will increase continually with time. The sample will show no plateau viscosity, although there may be a low shear viscous contribution. This applies to both a single Maxwell model and one with a spectrum of processes ... 

An important and sometimes overlooked feature of all linear viscoelastic liquids that follow a Maxwell response is that they exhibit anti-thixo-tropic behaviour. That is if a constant shear rate is applied to a material that behaves as a Maxwell model the viscosity increases with time up to a constant value. We have seen in the previous examples that as the shear rate is applied the stress progressively increases to a maximum value. The approach we should adopt is to use the Boltzmann Superposition Principle. Initially we apply a continuous shear rate until a steady state... 

You will notice that this is the expression for a Maxwell model (see Equation 4.25). From Equations (4.121) to (4.125) we have applied a Fourier transform and confirmed that a Maxwell model fits at least this portion of the theory of linear viscoelasticity. The simple expression for the relationship between J (co) and G (co) allows an interesting comparison to be performed. Suppose we take our equations for a Maxwell model and apply Equation (4.108) to transform the response to an oscillating strain into the response for an oscillating stress. This requires careful use of simple algebra to give... 

In the Maxwell model for viscoelastic deformation, it is assumed that the total strain is equal to the elastic strain plus the viscous strain. This is expressed in the two following differential equations from Equations 14.2 and 14.3. 

A further development is possible by noting that the high frequency shear modulus Goo is related to the mean square particle displacement (m ) of caged fluid particles (monomers) that are transiently localized on time scales ranging between an average molecular collision time and the structural relaxation time r. Specifically, if the viscoelasticity of a supercooled liquid is approximated below Ti by a simple Maxwell model in conjunction with a Langevin model for Brownian motion, then (m ) is given by [188]... 

The Maxwell Model. The first model of viscoelasticity was proposed by Maxwell in 1867, and it assumes that the viscous and elastic components occur in series, as in Figure 5.60a. We will develop the model for the case of shear, but the results are equally general for the case of tension. The mathematical development of the Maxwell model is fairly straightforward when we consider that the applied shear stress, r, is the same on both the elastic, Xe, and viscous, Xy, elements. 

Using a Maxwell model as a constitutive equation for a viscoelastic fluid, one can show that the instantaneous shear stress at the wall is smaller in the viscoelastic fluid than in the corresponding Newtonian fluid. 

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 body under drying is a moistened capillary-porous solid. This body is assumed here to be of isotropic structure and obeying the viscoelastic Maxwell model of the form... 

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. 

The models described so far provide a qualitative illustration of the viscoelastic behaviour of polymers. In that respect the Maxwell element is the most suited to represent fluid polymers the permanent flow predominates on the longer term, while the short-term response is elastic. The Kelvin-Voigt element, with an added spring and, if necessary, a dashpot, is better suited to describe the nature of a solid polymer. With later analysis of the creep of polymers, we shall, therefore, meet the Kelvin-Voigt model again in more detailed descriptions of the fluid state the Maxwell model is being used. 

Figure 2 Graphical representation of the Voigt-Kelvin model (a) and the Maxwell model (b) of viscoelasticity. rd is the retardation time and

The simplest model that can be used for describing a single creep experiment is the Burgers element, consisting of a Maxwell model and a Voigt-Kelvin model in series. This element is able to describe qualitatively the creep behaviour of viscoelastic materials... 

Though a simple Maxwell model in the form of equations (1) and (2) is powerful to describe the linear viscoelastic behaviour of polymer melts, it can do nothing more than what it is made for, that is to describe mechanical deformations involving only infinitesimal deformations or small perturbations of molecules towards their equilibrium state. But, as soon as finite deformations are concerned, which are typically those encountered in processing operations on pol rmers, these equations fail. For example, the steady state shear and elongational viscosities remain constant throughout the entire rate of strain range, normal stresses are not predicted. 

Both these models find their basis in network theories. The stress, as a response to flow, is assiimed to find its origin in the existence of a temporary network of junctions that may be destroyed by both time and strain effects. Though the physics of time effects might be complex, it is supposed to be correctly described by a generalized Maxwell model. This enables the recovery of a representative discrete time spectrum which can be easily calculated from experiments in linear viscoelasticity. 

Table 7 gives a summary of qualitative performances and problems encountered for simple shear and uniaxial elongational flows, using the Wagner and the Phan Thien Tanner equations or more simple models as special cases of the former. Additional information may also be found in papers by Tanner [46, 64]. All equations presented hereafter can be cast in the form of a linear Maxwell model in the small strain limit and therefore are suitable for the description of results of the linear viscoelasticity in the terminal zone of polymer melts. 

Three equations are basic to viscoelasticity (1) Newton s law of viscosity, a = ijy, (2) Hooke s law of elasticity. Equation 1.15, and (3) Newton s second law of motion, F = ma, where m is the mass and a is the acceleration. One can combine the three equations to obtain a basic differential equation. In linear viscoelasticity, the conditions are such that the contributions of the viscous, elastic, and the inertial elements are additive. The Maxwell model is ... 

Figure 1-8 Maxwell Model (Left) and Kelvin-Voigt Model (Right) Illustrate Mechanical Analogs of Viscoelastic Behavior.

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