Boltzmann superposition

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. 

Now consider the situation in which the stress, ai, was applied at time, ti, and an additional stress, Boltzmanns Superposition Principle states that the total strain at time, t, is the algebraic sum of the two independent responses. 

Fig. 2.44(b) Predicted strain response using Boltzmann s superposition principle... 

A plastic with a time dependent creep modulus as in the previous example is stressed at a linear rate to 40 MN/m in 100 seconds. At this time the stress in reduced to 30 MN/m and kept constant at this level. If the elastic and viscous components of the modulus are 3.5 GN/m and 50 x 10 Ns/m, use Boltzmann s Superposition Principle to calculate the strain after (a) 60 seconds and (b) 130 seconds. 

A plastic which behaves like a Kelvin-Voigt model is subjected to the stress history shown in Fig. 2.87. Use the Boltzmanns Superposition Principle to calculate the strain in the material after (a) 90 seconds (b) 150 seconds. The spring constant is 12 GN/m and the dashpot constant is 360 GNs/m. ... 

Object in this section is to review how rheological knowledge combined with laboratory data can be used to predict stresses developed in plastics undergoing strains at different rates and at different temperatures. The procedure of using laboratory experimental data for the prediction of mechanical behavior under a prescribed use condition involves two principles that are familiar to rheologists one is Boltzmann s superposition principle which enables one to utilize basic experimental data such as a stress relaxation modulus in predicting stresses under any strain history the other is the principle of reduced variables which by a temperature-log time shift allows the time scale of such a prediction to be extended substantially beyond the limits of the time scale of the original experiment. 

With crystalline plastics, the main effect of the crystallinity is to broaden the distribution of the relaxation times and extend the relaxation stress too much longer periods. This pattern holds true at both the higher and low extremes of crystallinity (Chapter 6). With some plastics, their degree of crystallinity can change during the course of a stress-relaxation test. This behavior tends to make the Boltzmann superposition principle difficult to apply. 

A creep test can be carried out with an imposed stress, then after a time have its stress suddenly changed to a new value and have the test continued. This type of change in loading allows the creep curve to be predicted. The simple law referred to earlier as the Boltzmann superposition principle, hold for most materials, so that their creep curves can thus be predicted. 

The first assumption involved in using the Boltzmann superposition principle is that elongation is proportional to stress, that is, compliance is independent of stress. The second assumption is that the elongation created by a given load is independent of the elongation caused by any previous load. Therefore, deformation resulting from a complex loading history is obtained as the sum of the deformations that can be attributed to each separate load. 

At low enough temperatures, only that substitutional isomer which has the lowest ZPVE will be populated. At higher temperatures, however, other isomers may also be found, so that a superposition of several spectra is observed in an ESR experiment. Previously, we have found [1-4] that the abundances of these other isomers are well predicted by a Boltzmann distribution based on the differences in ZPVE. Since the 6-31G(d) and 6-31 lG(d,p) basis sets gave very similar geometries in the present case (see below), the vibrational frequencies and ZPVE for the mono-deuterated isomers were calculated only at the B3-LYP/6-31G(d) level. 

Similar convection-diffusion equations to the Navier-Stokes equation can be formulated for enthalpy or species concentration. In all of these formulations there is always a superposition of diffusive and convective transport of a field quantity, supplemented by source terms describing creation or destruction of the transported quantity. There are two fundamental assumptions on which the Navier-Stokes and other convection-diffusion equations are based. The first and most fundamental is the continuum hypothesis it is assumed that the fluid can be described by a scalar or vector field, such as density or velocity. In fact, the field quantities have to be regarded as local averages over a large number of particles contained in a volume element embracing the point of interest. The second hypothesis relates to the local statistical distribution of the particles in phase space the standard convection-diffusion equations rely on the assumption of local thermal equilibrium. For gas flow, this means that a Maxwell-Boltzmann distribution is assumed for the velocity of the particles in the frame-of-reference co-moving with the fluid. Especially the second assumption may break dovm when gas flow at high temperature or low pressure in micro channels is considered, as will be discussed below. 

There are two superposition principles that are important in the theory of Viscoelasticity. The first of these is the Boltzmann superposition principle, which describes the response of a material to different loading histories (22). The second is the time-temperature superposition principle or WLF (Williams, Landel, and Ferry) equation, which describes the effect of temperature on the time scale of the response. 

The Boltzmann superposition principle states that the response of a material to a given load is independent of the response of the material to ary load that is already on the material. Another consequence of this principle is that the deformation of a specimen is directly proportional to the applied stress when all deformations are compared at equivalent, times... 

Figure 7 illustrates the Boltzmann superposition principle for a polymer that obeys a common type of behavior given by the Nutting equation... 

Figure 7 Creep of a material that obeys the Boltzmann superposition principle. The load is doubled after 400 s.

If the Boltzmann superposition principle holds, the creep strain is directly proportional to the stress at any given time, f Similarly, the stress at any given lime is directly proportional to the strain in stress relaxation. That is. the creep compliance and the stress relaxation modulus arc independent of the stress and slrai . respectively. This is generally true for small stresses or strains, but the principle is not exact. If large loads are applied in creep experiments or large strains in stress relaxation, as can occur in practical structural applications, nonlinear effects come into play. One result is that the response (0 l,r relaxation times can also change, and so can ar... 

The distribution of relaxation or retardation times is much broader for cystallinc than for amorphous polymers, the Boltzmann superposition... 

Assuming that the Boltzmann superposition principle holds for the polymer in Problem I, what would the creep elongation be from 100 to 10,000 min if the load were doubled after 100 min ... 

Assuming thai the Boltzmann superposition principle holds and that all of the creep is recoverable, what would the creep recovery curve be for I he polymer in Problem 1 if the load were removed after lO.(KM) min ... 

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 ... 

The ideal stress relaxation experiment is one in which the stress is instantaneously applied. We have seen in Section 4.4.2 the exponential relaxation that characterises the response of a Maxwell model. We can consider this experiment in detail as an example of the application of the Boltzmann Superposition Principle. The practical application of an instantaneous strain is very difficult to achieve. In a laboratory experi-... 

Let us suppose the strain applied at time t0 increases over a time v to a maximum value y. At times less than to — v no strain is applied and at times greater than t0 the strain is constant. This gives the limits to the Boltzmann superposition integral ... 

Now we can apply these conditions to the Boltzmann superposition integral (Equation 4.60) ... 

The application of a linearly ramped strain can provide information on both the sample elasticity and viscosity. The stress will grow in proportion to the applied strain. The ratio of the strain over the applied time gives the shear rate. Applying the Boltzmann Superposition Principle we obtain the following expression ... 

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... 

So far we have seen that if we begin with the Boltzmann superposition integral and include in that expression a mathematical representation for the stress or strain we apply, it is possible to derive a relationship between the instrumental response and the properties of the material. For an oscillating strain the problem can be solved either using complex number theory or simple trigonometric functions for the deformation applied. Suppose we apply a strain described by a sine wave ... 

Now in order to apply the Boltzmann Superposition Principle (Equation 4.60) we need to express this as a strain rate. Differentiating with respect to time gives us... 

Now the Boltzmann superposition integral is given by Equation (4.60). Substituting for the strain and replacing t by t in Equation (4.88) gives... 

Time Dependence in Flow and the Boltzmann Superposition Principle... 

Whilst the flow curves of materials have received widespread consideration, with the development of many models, the same cannot be said of the temporal changes seen with constant shear rate or stress. Moreover we could argue that after the apparent complexity of linear viscoeleastic systems the non-linear models developed above are very poor cousins. However, it is possible to introduce a little more phenomenological rigour by starting with the Boltzmann superposition integral given in Chapter 4, Equation (4.60). This represents the stress at time t for an applied strain history ... 

Several general methods are available for solving the diffusion equation, including Boltzmann transformation, principle of superposition, separation of... 

The one-dimensional diffusion equation in isotropic medium for a binary system with a constant diffusivity is the most treated diffusion equation. In infinite and semi-infinite media with simple initial and boundary conditions, the diffusion equation is solved using the Boltzmann transformation and the solution is often an error function, such as Equation 3-44. In infinite and semi-infinite media with complicated initial and boundary conditions, the solution may be obtained using the superposition principle by integration, such as Equation 3-48a and solutions in Appendix 3. In a finite medium, the solution is often obtained by the separation of variables using Fourier series. 

One of the simplest equations is obtained using the Debye-Hiickel approximation (for low potentials) and the superposition principle. The latter assumes that the unperturbed potential near a charged surface can be simply added to that potential due to the other (unperturbed) surface. Thus, for the example shown in the Figure 6.12, it follows that /m = 2 /d/2- This is precisely valid for Coulomb-type interactions, where the potential at any point can be calculated from the potentials produced by each fixed charge, individually. However, the Poisson-Boltzmann equation is non-linear (this has to do with the fact that in the diffuse double-layer the ions are not fixed but move because of their kinetic energy) and so this is formally not correct although it still offers a useful approximation. 

---