Linear viscoelastic behavior

In this approach the reviews concerned the rheology involving the linear viscoelastic behavior of plastics and how such behavior is affected by temperature. Next is to extend this knowledge to the complex behavior of crystalline plastics, and finally illustrate how experimental data were applied to a practical example of the long-time mechanical stability. 

There are several other comparable rheological experimental methods involving linear viscoelastic behavior. Among them are creep tests (constant stress), dynamic mechanical fatigue tests (forced periodic oscillation), and torsion pendulum tests (free oscillation). Viscoelastic data obtained from any of these techniques must be consistent data from the others. 

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 clear that this data treatment is strictly valid providing the tested material exhibits linear viscoelastic behavior, i.e., that the measured torque remains always proportional to the applied strain. In other words, when the applied strain is sinusoidal, so must remain the measured torque. The RPA built-in data treatment does not check this y(o )/S (o)) proportionality but a strain sweep test is the usual manner to verify the strain amplitude range for constant complex torque reading at fixed frequency (and constant temperature). 

J.L. Leblanc, Investigating the non-linear viscoelastic behavior of filled mbber compounds through Fourier transform rheometry. Rubber Chem. TechnoL, 78, 54—75, 2005. 

The linear viscoelastic behavior of liquid and solid materials in general is often defined by the relaxation time spectrum 11(1) [10], which will be abbreviated as spectrum in the following. The transient part of the relaxation modulus as used above is the Laplace transform of the relaxation time spectrum H(l)... 

N, W. Tschoegl, The Phenomenological Theory of Linear Viscoelastic Behavior, Springer-Verlag, New York, 1989. 

Contents Chain Configuration in Amorphous Polymer Systems. Material Properties of Viscoelastic Liquids. Molecular Models in Polymer Rheology. Experimental Results on Linear Viscoelastic Behavior. Molecular Entan-lement Theories of Linear iscoelastic Behavior. Entanglement in Cross-linked Systems. Non-linear Viscoelastic-Properties. 

The response of simple fluids to certain classes of deformation history can be analyzed. That is, a limited number of material functions can be identified which contain all the information necessary to describe the behavior of a substance in any member of that class of deformations. Examples are the viscometric or steady shear flows which require, at most, three independent functions of the shear rate (79), and linear viscoelastic behavior (80,81) which requires only a single function, in this case a relaxation function. The functions themselves must be determined experimentally for each substance. 

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) ... 

The mean times t and tw will be called the number-average and weight-average relaxation times of the terminal region, and tw/t can be regarded as a measure of the breadth of the terminal relaxation time distribution. It should be emphasized that these relationships are merely consequences of linear viscoelastic behavior and depend in no way on assumptions about molecular behavior. The observed relationships between properties such as rj0, J°, and G and molecular parameters provides the primary evidence for judging molecular theories of the long relaxation times in concentrated systems. 

Molecular Entanglement Theories of Linear Viscoelastic Behavior... 

The parallel between po and JeR has been noted elsewhere (208,213,328,329), and is not in fact fortuitous. It follows rather directly from the empirical observation that departures of t (y) and r/ (co) from t]0 are governed by the longest relaxation times of the system, combined with slight extensions of a reduced variables argument suggested by Markovitz for linear viscoelastic behavior (329). Suppose one wants to compare the forms of the dynamic moduli on... 

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. 

Forsman,W.C., Grand, H.S. Theory of entanglement effects in linear viscoelastic behavior of polymer solutions and melts. I. Symmetry considerations. Macromolecules 5,289-293 (1972). 

The question whether ammonia treated wood shows linear or non-linear viscoelastic behavior has not been answered so far. 

N2 values are always lower than Nj values, see e.g. [40]. Therefore for many processes taking into consideration only Nj will suffice. The normal stress differences are independent of the direction of flow and, in laminar flow (low y), are proportional to y2. In following p = x/y for a Newtonian fluid, normal stress coefficients ipi = Nj/y2 and ip2 = N2/y2 are occasionally used. Their dependence on the shear rate i j(y) describes the non-linear viscoelastic behavior of the fluid. 

Schwakzl, F., and A. J. Staverman Time-temperature dependence of linear viscoelastic behavior. J. Appl. Phys. 23, 838—843 (1952). 

The four variables in dynamic oscillatory tests are strain amplitude (or stress amplitude in the case of controlled stress dynamic rheometers), frequency, temperature and time (Gunasekaran and Ak, 2002). Dynamic oscillatory tests can thus take the form of a strain (or stress) amplitude sweep (frequency and temperature held constant), a frequency sweep (strain or stress amplitude and temperature held constant), a temperature sweep (strain or stress amplitude and frequency held constant), or a time sweep (strain or stress amplitude, temperature and frequency held constant). A strain or stress amplitude sweep is normally carried out first to determine the limit of linear viscoelastic behavior. In processing data from both static and dynamic tests it is always necessary to check that measurements were made in the linear region. This is done by calculating viscoelastic properties from the experimental data and determining whether or not they are independent of the magnitude of applied stresses and strains. 

Tschoegl NW (1989) The phenomenological theory of linear viscoelastic behavior. Springer, Berlin Heidelberg New York... 

On a global scale, the linear viscoelastic behavior of the polymer chains in the nanocomposites, as detected by conventional rheometry, is dramatically altered when the chains are tethered to the surface of the silicate or are in close proximity to the silicate layers as in intercalated nanocomposites. Some of these systems show close analogies to other intrinsically anisotropic materials such as block copolymers and smectic liquid crystalline polymers and provide model systems to understand the dynamics of polymer brushes. Finally, the polymer melt-brushes exhibit intriguing non-linear viscoelastic behavior, which shows strainhardening with a characteric critical strain amplitude that is only a function of the interlayer distance. These results provide complementary information to that obtained for solution brushes using the SFA, and are attributed to chain stretching associated with the space-filling requirements of a melt brush. 

In linear viscoelastic behavior the stress and strain both vary sinusoidally, although they may not be in phase with each other. Also, the stress amplitude is linearly proportional to the strain amplitude at given temperature and frequency. Then mechanical responses observed under different test conditions can be interrelated readily. The behavior of a material in one condition can be predicted from measurement made under different circumstances. 

Linear viscoelastic behavior is actually observed with polymers only in very restricted circumstances involving homogeneous, isotropic, amorphous specimens subjected to small strains at temperatures near or above Tg and under test conditions that are far removed from those in which the sample may be broken. Linear viscoelasticity theory is of limited use in predicting service behavior of polymeric articles, because such applications often involve large strains, anisotropic objects, fracture phenomena, and other effects which result in nonlinear behavior. The theory is nevertheless valuable as a reference frame for a wide range of applications, just as the thermodynamic equations for ideal solutions help organize the observed behavior of real solutions. 

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. 

Limitations to the effectiveness of mechanical models occur because actual polymers are characterized by many relaxation times instead of single values and because use of the models mentioned assumes linear viscoelastic behavior which is observed only at small levels of stress and strain. The linear elements are nevertheless useful in constructing appropriate mathematical expressions for viscoelastic behavior and for understanding such phenomena. 

At small stresses and strains, glassy PC exhibits linear viscoelastic behavior. The limit of applicability of the theory of linear viscoelasticity has been investigated by Yannas et al. over the temperature range 23 °C-130 °C. The critical strain at which, within the precision of their measurement, deviations from the linear theory occur has been found to diminish from about 1.2% at 23 °C to about 0.7 % at 130 °C. According to Jansson and Yannas the transition from linear to nonlinear viscoelastic behavior is marked by the onset of significant rotation around backbone bonds. 

The above equation is a one-dimensional model of linear viscoelastic behavior. It can be also written in terms of the relaxation modulus after noting that ... 

Frequency sweep studies in which G and G" are determined as a function of frequency (o)) at a fixed temperature. When properly conducted, frequency sweep tests provide data over a wide range of frequencies. However, if fundamental parameters are required, each test must be restricted to linear viscoelastic behavior. Figure 3-31... 

In this book, we review the most basic distinctions and similarities among the rheological (or flow) properties of various complex fluids. We focus especially on their linear viscoelastic behavior, as measured by the frequency-dependent storage and loss moduli G and G" (see Section 1.3.1.4), and on the flow curve— that is, the relationship between the "shear viscosity q and the shear rate y. The storage and loss moduli reveal the mechanical properties of the material at rest, while the flow curve shows how the material changes in response to continuous deformation. A measurement of G and G" is often the most useful way of mechanically characterizing a complex material, while the flow curve q(y ) shows how readily the material can be processed, or shaped into a useful product. The... 

In the ordered state, lamellar block copolymers frequently show departures from linear viscoelastic behavior at low strain amplitudes of around 1% (Rosedale and Bates 1990 Winey et al. 1993a). Homogeneous polymers, on the other hand, typically show departures... 

Here only noncrystalline symmetries, which are likely to play an important role in the linear viscoelastic behavior of materials, are considered. We follow Tschoegl s approach to this subject (5). Crystalline materials and their symmetries are described in many textbooks (6,7). In order to study how the symmetry of the system affects the number of independent components of Cijki, it is convenient to reduce the number of indices of both the stress and strain tensors. Following Voigt s formulation, the reduction is made by doing 11 -> 1, 22 2, 33 3, 12 -> 4, 23 -> 5, 13 6, so that... 

The transient experiments to which we referred in the preceding chapter provide information on the linear viscoelastic behavior of materials in the... 

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