Linear viscoelasticity superposition principle

The simplest theoretical model proposed to predict the strain response to a complex stress history is the Boltzmann Superposition Principle. Basically this principle proposes that for a linear viscoelastic material, the strain response to a complex loading history is simply the algebraic sum of the strains due to each step in load. Implied in this principle is the idea that the behaviour of a plastic is a function of its entire loading history. There are two situations to consider. 

It is apparent therefore that the Superposition Principle is a convenient method of analysing complex stress systems. However, it should not be forgotten that the principle is based on the assumption of linear viscoelasticity which is quite inapplicable at the higher stress levels and the accuracy of the predictions will reflect the accuracy with which the equation for modulus (equation (2.33)) fits the experimental creep data for the material. In Examples (2.13) and (2.14) a simple equation for modulus was selected in order to illustrate the method of solution. More accurate predictions could have been made if the modulus equation for the combined Maxwell/Kelvin model or the Standard Linear Solid had been used. 

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... 

Viscoelastic behavior is classified as linear or non-linear according to the manner by which the stress depends upon the imposed deformation history (SO). Insteady shear flows, for example, the shear rate dependence of viscosity and the normal stress functions are non-linear properties. Linear viscoelastic behavior is obtained for simple fluids if the deformation is sufficiently small for all past times (infinitesimal deformations) or if it is imposed sufficiently slowly (infinitesimal rate of deformation) (80,83). In shear flow under these circumstances, the normal stress differences are small compared to the shear stress, and the expression for the shear stress reduces to a statement of the Boltzmann superposition principle (15,81) ... 

Apply the Boltzmann superposition principle for the case of a continuous stress application on a linear viscoelastic material to obtain the resulting strain y(t) in terms of J(t — t ) and ih/dt, the stress history. Consider the applied stress in terms of small applied At,-, as shown on the accompanying figure. 

With all these models, the simple ones as well as the spectra, it has to be supposed that stress and strain are, at any time, proportional, so that the relaxation function E(t) and the creep function D(t) are independent of the levels of deformation and stress, respectively. When this is the case, we have linear viscoelastic behaviour. Then the so-called superposition principle holds, as formulated by Boltzmann. This describes the effect of changes in external conditions of a viscoelastic system at different points in time. Such a change may be the application of a stress or also an imposed deformation. 

Later on we shall see that the superposition principle is is, for polymers, only seldomly obeyed linear viscoelasticity is only met at very small stresses and deformations, at loading levels occurring in practice the behaviour may strongly deviate from linearity. However, the superposition principle provides a useful first-order approximation. 

The major features of linear viscoelastic behavior that will be reviewed here are the superposition principle and time-temperature equivalence. Where they are valid, both make it possible to calculate the mechanical response of a material under a wide range of conditions from a limited store of experimental information. 

One must note that the balance equations are not dependent on either the type of material or the type of action the material undergoes. In fact, the balance equations are consequences of the laws of conservation of both linear and angular momenta and, eventually, of the first law of thermodynamics. In contrast, the constitutive equations are intrinsic to the material. As will be shown later, the incorporation of memory effects into constitutive equations either through the superposition principle of Boltzmann, in differential form, or by means of viscoelastic models based on the Kelvin-Voigt or Maxwell models, causes solution of viscoelastic problems to be more complex than the solution of problems in the purely elastic case. Nevertheless, in many situations it is possible to convert the viscoelastic problem into an elastic one through the employment of Laplace transforms. This type of strategy is accomplished by means of the correspondence principle. 

In linear elasticity or viscoelasticity, the superposition principle states that the resulting effects of the different causes (stress or displacements), acting separately, can be superposed to give the total values due to these combined causes. This principle is a consequence of the linearity of the equations governing the stress, strain, and displacements. 

Chapters 5 and 6 discuss how the mechanical characteristics of a material (solid, liquid, or viscoelastic) can be defined by comparing the mean relaxation time and the time scale of both creep and relaxation experiments, in which the transient creep compliance function and the transient relaxation modulus for viscoelastic materials can be determined. These chapters explain how the Boltzmann superposition principle can be applied to predict the evolution of either the deformation or the stress for continuous and discontinuous mechanical histories in linear viscoelasticity. Mathematical relationships between transient compliance functions and transient relaxation moduli are obtained, and interrelations between viscoelastic functions in the time and frequency domains are given. 

Materials can show linear and nonlinear viscoelastic behavior. If the response of the sample (e.g., shear strain rate) is proportional to the strength of the defined signal (e.g., shear stress), i.e., if the superposition principle applies, then the measurements were undertaken in the linear viscoelastic range. For example, the increase in shear stress by a factor of two will double the shear strain rate. All differential equations (for example, Eq. (13)) are linear. The constants in these equations, such as viscosity or modulus of rigidity, will not change when the experimental parameters are varied. As a consequence, the range in which the experimental variables can be modified is usually quite small. It is important that the experimenter checks that the test variables indeed lie in the linear viscoelastic region. If this is achieved, the quality control of materials on the basis of viscoelastic properties is much more reproducible than the use of simple viscosity measurements. Non-linear viscoelasticity experiments are more difficult to model and hence rarely used compared to linear viscoelasticity models. 

Linear Viscoelasticity of Unfractionated Samples. The BP6L and BP6H samples were found to give reproducible data at temperatures below 120°C if first exposed to 150°C for 5 minutes. After such a heat treatment measurements were made on these samples at T = 35, 41, 50, 60, 70, 80, 90, 101, and 120°C. The empirical time-temperature superposition principle (13) was found to be valid for BP6L between 60°C and 120°C and for BP6H between 40°C and 120°C, and was used to make master curves at a reference temperature of 101°C (Figs. 4 and 5). The modulus scale... 

The second important consequence of the relaxation times of all modes having the same temperature dependence is the expectation that it should -bp possible to superimpose linear viscoelastic data taken at different temperatures. This is commonly known as the time-temperature superposition principle. Stress relaxation modulus data at any given temperature Tcan be superimposed on data at a reference temperature Tq using a time scale multiplicative shift factor uj- and a much smaller modulus scale multiplicative shift factor hf. 

Inherent in the mathematical treatment of linear viscoelasticity is the Boltzmann superposition principle (15), which, in simple terms, states that the deformation resulting at any time is directly proportional to the applied stress. This is illustrated in Figure 10.5. 

Any of equations (2-45), (2-46), (2-49), or (2-50) is sufficient as a statement of the Boltzmann superposition principle for linear viscoelastic response of a material. Often in particular applications, however, it is more convenient to use one form than another. All can be extended to three dimensions by using the same forms with the strains given by equation (2-18). Thus, for example, equation (2-46) becomes ... 

In spite of these complications, the viscoelastic response of an amorphous polymer to small stresses turns out to be a relatively simple subject because of two helpful features (1) the behavior is linear in the stress, which permits the application of the powerful superposition principle and (2) the behavior often follows a time-temperature equivalence principle, which permits the rapid viscoelastic response at high temperatures and the slow response at low temperatures to be condensed in a single master curve. 

The basic foundation of linear viscoelasticity theory is the Boltzmann s superposition principle which states ... 

This idea can be used to formulate an integral representation of linear viscoelasticity. The strategy is to perform a thought experiment in which a step function in strain is applied, e t) = Cq H t), where H t) is the Heaviside step function, and the stress response a t) is measured. Then a stress relaxation modulus can be defined by E t) = <7(t)/ o Note that does not have to be infinitesimal due to the assumed superposition principle. To develop a model capable of predicting the stress response from an arbitrary strain history, start by decomposing the strain history into a sum of infinitesimal strain increments ... 

Another interesting aspect of linear viscoelasticity is that it can be extended to enable predictions at different temperatures. The basis for this approach is based on a time-temperature superposition principle.This approach has been shown to work well in a restricted temperature range, but does not change the requirement of small strains. 

Validity of Eqs 7.81 and 7.82 was examined for mixtures of entangled, nearly monodispersed blends of poly(ethylene-a/r-propylene) with head-to-head PP [Gell et al., 1997]. The viscoelastic properties compared at constant distance from the glass transition temperature of each system were found to obey the time-temperature superposition principle. The data agreed better with the predictions of Eq 7.82 than Eq 7.81. However, for blends of linear and branched PE the relations 7.82 were found valid only when MW and rheological properties of the two components were similar [Groves et al., 1996]. 

Linear viscoelasticity is the simplest viscoelastic behavior in which the ratio of stress to strain is a function of time alone and not of the strain or stress magnitude. Under a sufficiently small strain, the molecular structure will be practically unaffected, and linear viscoelastic behavior will be observed. At this sufficiently small strain (within the linear range), a general equation that describes all types of linear viscoelastic behavior can be developed by using the Boltzmann superposition principle (Dealy and Wiss-brun, 1990). For a sufficiently small strain (yo) in the experiment, the relaxation modulus is given by... 

In the following sections we discuss the two superposition principles that are important in the theory of viscoelasticity. The first is the Boltzmann superposition principle, which is concerned with linear viscoelasticity, and the second is time-temperature superposition, which deals with the time-temperature equivalence. 

Fortunately for linear amorphous polymers, modulus is a function of time and temperature only (not of load history). Modulus-time and modulus-temperature curves for these polymers have identieal shapes they show the same regions of viscoelastic behavior, and in each region the modulus values vary only within an order of magnitude. Thus, it is reasonable to assume from such similarity in behavior that time and temperature have an equivalent effect on modulus. Such indeed has been found to be the case. Viscoelastic properties of linear amorphous polymers show time-temperature equivalence. This constitutes the basis for the time-temperature superposition principle. The equivalence of time and temperature permits the extrapolation of short-term test data to several decades of time by carrying out experiments at different temperatures. 

The most commonly used model is the Boltzmann superposition principle, which proposes that for a linear viscoelastic material the entire loading history contributes to the strain response, and the latter is simply given by the algebraic sum of the strains due to each step in the load. The principle may be expressed as follows. If an equation for the strain is obtained as a function of time under a constant stress, then the modulus as a function of time may be expressed as... 

First, we need a rule to predict the effect of time-varying loads on a viscoelastic model. When a combination of loads is applied to an elastic material, the stress (and strain) components caused by each load in turn can be added. This addition concept is extended to linear viscoelastic materials. The Boltzmann superposition principle states that if a creep stress ai is... 

Boltzmann superposition principle A basis for the description of all linear viscoelastic phenomena. No such theor) is available to serve as a basis for the interpretation of nonlinear phenomena—to describe flows in which neither the strain nor the strain rate is small. As a result, no general valid formula exists for calculating values for one material function on the basis of experimental data from another. However, limited theories have been developed. See kinetic theory viscoelasticity, nonlinear, bomb See plasticator safety. 

We have used the generalized phenomenological Maxwell model or Boltzmann s superposition principle to obtain the basic equation (Eq. (4.22) or (4.23)) for describing linear viscoelastic behavior. For the kind of polymeric liquid studied in this book, this basic equation has been well tested by experimental measurements of viscoelastic responses to different rate-of-strain histories in the linear region. There are several types of rate-of-strain functions A(t) which have often been used to evaluate the viscoelastic properties of the polymer. These different viscoelastic quantities, obtained from different kinds of measurements, are related through the relaxation modulus G t). In the following sections, we shall show how these different viscoelastic quantities are expressed in terms of G(t) by using Eq. (4.22). 

In summary, if G t), which is contained in Eqs. (4.30), (4.34)-(4.37), (4.49)-(4.51), (4.63) and (4.73), is known, all the linear viscoelastic quantities can be calculated. In other words, all the various viscoelastic properties of the polymer are related to each other through the relaxation modulus G t). This result is of course the consequence of the generalized Maxwell equation or equivalently Boltzmann s superposition principle. The experimental results of linear viscoelastic properties of various polymers support the phenomenological principle. Some viscoelastic properties play more important roles than the others in certain rheological processes related to... 

Nonlinear viscoelasticity is the behavior in which the relationship of stress, strain, and time are not linear so that the ratios of stress to strain are dependent on the value of stress. (The Boltzmann superposition principle does not hold). Such behavior is very common in plastic systems, non-linearity being found especially at high strains or in crystalline plastics. 

Smce the Zener model is a linear viscoelastic model, it obeys the Boltz-mann superposition principle. In this problem we are concerned with a strain history which is a smooth varying function of time, with y undergoing sinusoidal oscillations. Therefore the integral form of the BSP is the most straightforward one to apply ... 

Use the integral form of the Boltzmann superposition principle to show that the creep compliance and stress relaxation modulus of any linear viscoelastic material are related through... 

Linear viscoelasticity is an extension of linear elasticity and hyperelasticity that enables predictions of time dependence and viscoelastic flow. Linear viscoelasticity has been extensively studied both mathematically (Christensen 2003) and experimentally (Ward and Hadley 1993), and can be very useful when applied under the appropriate conditions. Linear viscoelasticity models are available in all major commercial FE packages and are relatively easy to use. The basic foundation of linear viscoelasticity theory is the Boltzmann s superposition principle, which states, "Every loading step makes an independent contribution to the final state."... 

In linear viscoelasticity the stress relaxation test is often used, along with the time-temperature superposition principle and the Boltzmann superposition principle,... 

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