Linear Viscoelastic Experiments

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  

Now suppose at a time t later we apply another stress o. The strain will respond to this additional stress. This can be predicted by adding the result of this additional stress on the strain at a time t — tx later  

It should be remembered that ox = 0 while t t. This linear superposition of stresses can be generalised to any number of applied stresses  

The sum in this expression can be replaced by an integral which will enable us to describe the strain response to any stress history  

These two mathematical Equations (4.59) and (4.60) illustrate an important feature about linear viscoelastic measurements, i.e. the central role played by the relaxation function and the compliance. These terms can be used to describe the response of a material to any deformation history. If these can be modelled in terms of the chemistry of the system the complete linear rheological response of our material can be obtained. 

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Time-temperature superposition [10] increases the accessible frequency window of the linear viscoelastic experiments. It applies to stable material states where the extent of reaction is fixed ( stopped samples ). Winter and Chambon [6] and Izuka et al. [121] showed that the relaxation exponent n is independent of temperature and that the front factor (gel stiffness) shifts with temperature... 

Both Je° and rj0 can be evaluated from the response in other linear viscoelastic experiments also. 

Other types of linear viscoelastic experiments may be used. Dynamic shear compliance measurements provide the storage and loss compliances J (co) and J"(co). An equation analogous to Eq.(3.12) is available for determining the initial modulus from J"(co) ... 

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 stress relaxation modulus then decays exponentially at the reptation time [Eq. (9.22)]. The terminal relaxation time can be measured quite precisely in linear viscoelastic experiments. Hence, Eq. (9.82) provides the simplest direct means of testing the Doi fluctuation model and evaluating... 

Viscoelasticity will clearly have a large effect in some processing operations and little or none in others, and we require a way to discriminate between these cases. One clue follows from the linear viscoelastic experiments shown in Figures 9.2 and 9.3 and the accompanying spectral description in Equations 9.11a-b. The entangled network is able to relax at low frequencies, so the elastic contribution to the stress is negligible and the deformation is mostly dissipative (G 0). The stress at high fre-... 

A number of small strain experiments are used in rheology. Some of the more common techniques are stress relaxation, creep, and sinusoidal oscillations. In the linear viscoelastic region all small strain experiments must be related to one another through G(t), as indicated by the basic constitutive equation, eq. 3.2.7, or through M(t), eq. 3.2.4. Different experimental methods are used because they may be more convenient or better suited for a particular material or because they provide data over a particular time range. Furthermore, it is often not easy to transform results from one type of linear viscoelastic experiment to another. For example, transformation from the creep compliance J t) to the stress relaxation modulus G(t) is generally difficult. Thus both functions are often measured. 

The distribution of relaxation time and that of retardation time are quantitatively related. Also, the result from any linear viscoelastic experiment is quantitatively related to distribution of relaxation or retardation time. Therefore, from the result of one type of linear viscoelastic measurement, the data of any other type of measurement can be calculated, provided the data are available for a wide range of time scales. For example, dynamic shear storage modulus, G (a>) and dynamic shear loss modulus, G"(co), may be calculated from relaxation modulus, G(t). The method of calculation is described in textbooks [6] and outside of scope of this book. The importance here is to recognise that the distribution of the relaxation time is related to every data of linear viscoelasticity. 

The premise of the above analysis is the fact that it has treated the interfacial and bulk viscoelasticity equally (linearly viscoelastic experiencing similar time scales of relaxation). Falsafi et al. make an assumption that the adhesion energy G is constant in the course of loading experiments and its value corresponds to the thermodynamic work of adhesion W. By incorporating the time-dependent part of K t) into the left-hand side (LHS) of Eq. 61 and convoluting it with the evolution of the cube of the contact radius in the entire course of the contact, one can generate a set of [LHS(t), P(0J data. By applying the same procedure described for the elastic case, now the set of [LHS(t), / (Ol points can be fitted to the Eq. 61 for the best values of A"(I) and W. 

From such curves, however, it would not be possible to determine whether the viscoelasticity is in fact linear. An experiment is needed where the time effect can be isolated. Typical of such experiments is stress relaxation. In this test, the specimen is strained to a specified magnitude at the beginning of the test and held unchanged throughout the experiment, while the monotonically decay-... 

At sufficiently low strain, most polymer materials exhibit a linear viscoelastic response and, once the appropriate strain amplitude has been determined through a preliminary strain sweep test, valid frequency sweep tests can be performed. Filled mbber compounds however hardly exhibit a linear viscoelastic response when submitted to harmonic strains and the current practice consists in testing such materials at the lowest permitted strain for satisfactory reproducibility an approach that obviously provides apparent material properties, at best. From a fundamental point of view, for instance in terms of material sciences, such measurements have a limited meaning because theoretical relationships that relate material structure to properties have so far been established only in the linear viscoelastic domain. Nevertheless, experience proves that apparent test results can be well reproducible and related to a number of other viscoelastic effects, including certain processing phenomena. 

C. Friedrich, K. Mattes, and D. Schulze, Non-linear Viscoelastic Properties of Polymer Melts as Analyzed by LAOS-FT Experiments, lUPAC Macro 2004, Paris, France, July 4—9, 2004, Paper 6.1.3. 

Typical for the spectroscopic character of the measurement is the rapid development of a quasi-steady state stress. In the actual experiment, the sample is at rest (equilibrated) until, at t = 0, oscillatory shear flow is started. The shear stress response may be calculated with the general equation of linear viscoelasticity [10] (introducing Eqs. 4-3 and 4-9 into Eq. 3-2)... 

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... 

Firstly, it helps to provide a cross-check on whether the response of the material is linear or can be treated as such. Sometimes a material is so fragile that it is not possible to apply a low enough strain or stress to obtain a linear response. However, it is also possible to find non-linear responses with a stress/strain relationship that will allow satisfactory application of some of the basic features of linear viscoelasticity. Comparison between the transformed data and the experiment will indicate the validity of the application of linear models. 

The constant Tr is called the Trouton ratio10 and has a value of 3 in this experiment with an incompressible fluid in the linear viscoelastic limit. The elongational behaviour of fluids is probably the most significant of the non-shear parameters, because many complex fluids in practical applications are forced to extend and deform. Studying this parameter is an area of great interest for theoreticians and experimentalists. 

In order to observe linear viscoelasticity, structural relaxation by diffusion must occur on a timescale comparable to our measurement time. The ratio of these times is the Deborah number. When this is of the order of unity our experiment will follow the relaxation processes in the material and the material will appear to be viscoelastic ... 

The mechanical response of polypropylene foam was studied over a wide range of strain rates and the linear and non-linear viscoelastic behaviour was analysed. The material was tested in creep and dynamic mechanical experiments and a correlation between strain rate effects and viscoelastic properties of the foam was obtained using viscoelasticity theory and separating strain and time effects. A scheme for the prediction of the stress-strain curve at any strain rate was developed in which a strain rate-dependent scaling factor was introduced. An energy absorption diagram was constructed. 14 refs. 

It appears that the formal theories are not sufficiently sensitive to structure to be of much help in dealing with linear viscoelastic response Williams analysis is the most complete theory available, and yet even here a dimensional analysis is required to find a form for the pair correlation function. Moreover, molecular weight dependence in the resulting viscosity expression [Eq. (6.11)] is much too weak to represent behavior even at moderate concentrations. Williams suggests that the combination of variables in Eq. (6.11) may furnish theoretical support correlations of the form tj0 = f c rjj) at moderate concentrations (cf. Section 5). However the weakness of the predicted dependence compared to experiment and the somewhat arbitrary nature of the dimensional analysis makes the suggestion rather questionable. 

The Eyring analysis does not explicity take chain structures into account, so its molecular picture is not obviously applicable to polymer systems. It also does not appear to predict normal stress differences in shear flow. Consequently, the mechanism of shear-rate dependence and the physical interpretation of the characteristic time t0 are unclear, as are their relationships to molecular structure and to cooperative configurational relaxation as reflected by the linear viscoelastic behavior. At the present time it is uncertain whether the agreement with experiment is simply fortuitous, or whether it signifies some kind of underlying unity in the shear rate dependence of concentrated systems of identical particles, regardless of their structure and the mechanism of interaction. 

Thus, we may give a good description of a linear viscoelastic material in terms of relaxed, and unrelaxed elastic constants and a distribution of relaxation times (- this is not necessarily the same distribution for each elastic constant ). These all have to be found from experiments. In general it is possible to find some of the relaxed and unrelaxed elastic constants and to estimate the distribution of relaxation times. 

Our reason for stressing the concept of representative volume element is that it seems to provide a valuable dividing boundary between continuum theories and molecular or microscopic theories. For scales larger than the RVE we can use continuum mechanics (classical and large strain elasticity, linear and non-linear viscoelasticity) and derive from experiment useful and reproducible properties of the material as a whole and of the RVE in particular. Below the scale of the RVE we must consider the micromechanics if we can - which may still be analysable by continuum theories but which eventually must be studied by the consideration of the forces and displacements of polymer chains and their interactions. 

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