Superposition principle defined

Another important characteristic aspect of systems near the glass transition is the time-temperature superposition principle [23,34,45,46]. This simply means that suitably scaled data should all fall on one common curve independent of temperature, chain length, and time. Such generahzed functions which are, for example, known as generalized spin autocorrelation functions from spin glasses can also be defined from computer simulation of polymers. Typical quantities for instance are the autocorrelation function of the end-to-end distance or radius of gyration Rq of a polymer chain in a suitably normalized manner ... 

II. Principles of Quantum Mechanics. This section defines the state of a system, the wave function, the Schrddinger equation, the superposition principle and the different representations. It can be given with or without calculus and with or without functional analysis, depending on the mathematical preparation of the students. Additional topics include ... 

There are many types of deformation and forces that can be applied to material. One of the foundations of viscoelastic theory is the Boltzmann Superposition Principle. This principle is based on the assumption that the effects of a series of applied stresses acting on a sample results in a strain which is related to the sum of the stresses. The same argument applies to the application of a strain. For example we could apply an instantaneous stress to a body and maintain that stress constant. For a viscoelastic material the strain will increase with time. The ratio of the strain to the stress defines the compliance of the body ... 

A complete comprehension of Single Pulse electrochemical techniques is fundamental for the study of more complex techniques that will be analyzed in the following chapters. Hence, the concept of half-wave potential, for example, will be defined here and then characterized in all electrochemical techniques [1, 3, 8]. Moreover, when very small electrodes are used, a stationary current-potential response is reached. This is independent of the conditions of the system prior to each potential step and even of the way the current-potential was obtained (i.e., by means of a controlled potential technique or a controlled current one) [9, 10]. So, the stationary solutions deduced in this chapter for the current-potential curves for single potential step techniques are applicable to any multipotential step or sweep technique such as Staircase Voltammetry or Cyclic Voltammetry. Moreover, many of the functional dependences shown in this chapter for different diffusion fields are maintained in the following chapters when multipulse techniques are described if the superposition principle can be applied. 

This is none other than the time-temperature superposition principle. However, the exact shape of the function F(t) is not a generic feature of the theory. A good approximation is provided by the Kohlrausch stretched exponential function. In the frequency domain, Eqs. (23) define the shape of the susceptibility minimum usually observed in the gigahertz range, and an interpolation formula follows ... 

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. 

The Boltzmann superposition principle is one of the simplest but most powerful principles of polymer physics.2 We have previously defined the shear creep compliance as relating the stress and strain in a creep experiment. Solving equation (2-6) for strain gives... 

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 ... 

Since Pp-parameters like P-fimction have wave properties, the superposition principles should be fulfilled for them, defining the linear character of the equations of adding and changing P-parameter. 

We can apply the superposition principle to calculate the image held i x, y, z) corresponding to the extended object field o(xo, yo, zo) defined on the plane region Eq, obtaining... 

The time-temperature superposition principle can be incorporated into isothermal constitutive equations (including the generalized Newtonian fluid model) to solve non-isothermal flow problems. If we define... 

Once modifications to functions of this kind have been made, the Boltzmann superposition principle can no longer be assumed to apply, and there is no simple replacement for it. This marks a significant change in the level of difficulty when moving from linear to non-linear theory. In the linear case, the material behaviour is defined fully by single-step creep and stress relaxation, and the result of any other stress or strain history then can be calculated using the Boltzmann integral. In the non-linear case we have lost the Boltzmann equation, and it is not even clear what measurements are needed for a full definition of the material. 

Another simple adaptation of the Boltzmann superposition principle is that of Findlay and Lai [14], who worked with step stress histories applied to specimens of poly(vinylchloride). Their theory was reformulated by Pipkin and Rogers [15] for general stress and strain histories. Pipkin and Rogers took a non-linear stress relaxation modulus R t, e), defined somewhat differently from G in Equation (10.4) ... 

In the course of tensile creep, the form of the time dependence of strain (as expressed by the stretch ratio X, for example) depends on the magnitude of tensile stress at high stresses." " Recovery is considerably more rapid than would be predicted from the Boltzmann superposition principle, as illustrated in Fig. 13-23 for polyisobutylene of high molecular weight. " The course of recovery is predicted successfully by the theory of Bernstein, Kearsley, and Zapas. 2 - 22 -pije stress-dependent recoverable steady-state compliance D = which is equal to Z) at low stresses, decreases with increasing Ot- This effect, moderate when the tensile strain e is defined as X — 1, is more pronounced when it is replaced by the Hencky strain, defined as In X. The stress dependence of steady-state compliance in shear will be discussed in Chapter 17. The reader is referred to the review by Petrie" for more details. 

The effects of a number of environmental factors on viscoelastic material properties can be represented by a time shift and thus a shift factor. In Chapter 10, a time shift associated with stress nonlinearities, or a time-stress-superposition-principle (TSSP), is discussed in detail both from an analytical and an experimental point of view. A time scale shift associated with moisture (or a time-moisture-superposition-principle) is also discussed briefly in Chapter 10. Further, a time scale shift associated with several environmental variables simultaneously leading to a time scale shift surface is briefly mentioned. Other examples of possible time scale shifts associated with physical and chemical aging are discussed in a later section in this chapter. These cases where the shift factor relationships are known enables the constitutive law to be written similar to Eq. 7.53 with effective times defined as in Eq. 7.54 but with new shift factor functions. This approach is quite powerful and enables long-term predictions of viscoelastic response in changing environments. 

Define and describe the time-temperature-superposition principle. 

In defining the constitutive relations for an elastic solid, we have assumed that the strains are small and that there are linear relationships between stress and strain. We now ask how the principle of linearity can be extended to materials where the deformations are time dependent. The basis of the discussion is the Boltzmann superposition principle. This states that in linear viscoelasticity effects are simply additive, as in classical elasticity, the difference being that in linear viscoelasticity it matters at which instant an effect is created. Although the application of stress may now cause a time-dependent deformation, it can still be assumed that each increment of stress makes an independent contribution. From the present discussion, it can be seen that the linear viscoelastic theory must also contain the additional assumption that the strains are small. In Chapter 11, we will deal with attempts to extend linear viscoelastic theory either to take into account non-linear effects at small strains or to deal with the situation at large strains. 

The Boltzmann superposition principle is one starting point for a theory of linear viscoelastic behaviour, and is sometimes called the integral representation of linear viscoelasticity , because it defines an integral equation. An equally valid starting point is to relate the stress to the strain by a linear differential equation, which leads to a differential representation of linear viscoelasticity. In its most general form, the equation is expressed as... 

In Chapter 5, we introduced linear viscoelasticity. In this scheme, the observed creep or stress relaxation behaviour can be viewed as the defining characteristic of the material. The creep compliance function - the ratio of creep strain e t) to the constant stress a - is a function of time only and is denoted as J t). Similarly and necessarily, the stress relaxation modulus, the ratio of stress to the constant strain, is the function G(r). Any system in which these two conditions do not apply is non-linear. Then, the many useful and elegant properties associated with the linear theory, notably the Boltzmann superposition principle, no longer apply and theories to predict stress or strain are approximations that must be supported by experiment. 

For composites, the time-dependent mechanical responses at a temperature T can be shifted onto the responses at a reference temperature based on the time-temperature superposition principle using the time-temperature shift factor. The time-temperature shift factor o,. (7) is defined by ... 

A corner-stone of the theory of linear viscoelasticity is the Boltzmann superposition principle. It allows the state of stress or strain in a viscoelastic body to be determined from knowledge of its entire deformation history. The basic assumption is that during viscoelastic deformation in which the applied stress is varied, the overall deformation can be determined from the algebraic sum of strains due to each loading step. Before the use of the principle can be demonstrated it is necessary, first of all, to define a parameter known as the creep compliance J(t) which is a function only of time. It allows the strain after a given time e(t) to be related to the applied stress or for a linear viscoelastic material since... 

It is possible to analyse stress relaxation in a similar way using the Boltzmann superposition principle. In this case it is necessary to define a stress relaxation modulus G(t) which relates the time-dependent stress a(t) to the strain e through the relationship... 

Oppenheim [1954] (cf. also Friedman and Oppenheim [1955]) has used the expansion method in powers of to express the deviations of the partition function from its classical value in terms of integrals which involve the molecular distribution functions defined in Ch. V. He then uses Kirkwood s superposition principle [1935] to estimate the radial distribution function. 

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