Mechanical behavior linear viscoelasticity

Mechanical properties of plastics are invariably time-dependent. Rheology of plastics involves plastics in all possible states from the molten state to the glassy or crystalline state (Chapter 6). The rheology of solid plastics within a range of small strains, within the range of linear viscoelasticity, has shown that mechanical behavior has often been successfully related to molecular structure. Studies in this area can have two objectives (1) mechanical characterization of... 

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. 

Since these double-base proplnts consist essentially of a single phase which bears the total load in any application of force, their mechanical property behavior is significantly different from composite proplnts. In the latter formulations, the hydrocarbon binder comprises only about 14% of the composite structure, the remainder being solid particles. Under stress, the binder of these proplnts bears a proportionately higher load than that in the single phase double-base proplnts. At small strain levels, these proplnts behave in a linear viscoelastic manner where the solids reinforce the binder. As strain increases, the bond between the oxidizer and binder breaks down... 

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. 

Researchers have examined the creep and creep recovery of textile fibers extensively (13-21). For example, Hunt and Darlington (16, 17) studied the effects of temperature, humidity, and previous thermal history on the creep properties of Nylon 6,6. They were able to explain the shift in creep curves with changes in temperature and humidity. Lead-erman (19) studied the time dependence of creep at different temperatures and humidities. Shifts in creep curves due to changes in temperature and humidity were explained with simple equations and convenient shift factors. Morton and Hearle (21) also examined the dependence of fiber creep on temperature and humidity. Meredith (20) studied many mechanical properties, including creep of several generic fiber types. Phenomenological theory of linear viscoelasticity of semicrystalline polymers has been tested with creep measurements performed on textile fibers (18). From these works one can readily appreciate that creep behavior is affected by many factors on both practical and theoretical levels. 

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. 

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. 

Dynamic mechanical measurements are performed at very small strains in order to ensure that linear viscoelasticity relations can be applied to the data. Stress-strain data involve large strain behavior and are accumulated in the nonlinear region. In other words, the tensile test itself alters the structure of the test specimen, which usually cannot be cycled back to its initial state. (Similarly, dynamic deformations at large strains test the fatigue resistance of the material.)... 

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... 

Polymeric fluids are the most studied of all complex fluids. Their rich rheological behavior is deservedly the topic of numerous books and is much too vast a subject to be covered in detail here. We must therefore limit ourselves to an overview. The interested reader can obtain more thorough presentations in the following references a book by Ferry (1980), which concentrates on the linear viscoelasticity of polymeric fluids, a pair of books by Bird et al. (1987a,b), which cover polymer constitutive equations, molecular models, and elementary fluid mechanics, books by Tanner (1985), by Dealy and Wissbrun (1990), and by Baird and Dimitris (1995), which emphasize kinematics and polymer processing flows, a book by Macosko (1994) focusing on measurement methods and a book by Larson (1988) on polymer constitutive equations. Parts of this present chapter are condensed versions of material from Larson (1988). The static properties of flexible polymer molecules are discussed in Section 2.2.3 their chemistry is described in Flory (1953). 

Because of the interaction of the two complicated and not well-understood fields, turbulent flow and non-Newtonian fluids, understanding of DR mechanism(s) is still quite limited. Cates and coworkers (for example, Refs. " ) and a number of other investigators have done theoretical studies of the dynamics of self-assemblies of worm-like micelles. Because these so-called living polymers are subject to reversible scission and recombination, their relaxation behavior differs from reptating polymer chains. An additional form of stress relaxation is provided by continuous breaking and repair of the micellar chains. Thus, stress relaxation in micellar networks occurs through a combination of reptation and breaking. For rapid scission kinetics, linear viscoelastic (Maxwell) behavior is predicted and is observed for some surfactant systems at low frequencies. In many cationic surfactant systems, however, the observed behavior in Cole-Cole plots does not fit the Maxwell model. 

It is common to compare the behavior of polymers with the behavior of metals and to use similar types of experiments to evaluate their performance under mechanical deformation. It is, therefore, important to highlight any qualitatively significant differences between their behavior and the fundamental physical reasons for these differences. In metals, creep is neither linearly viscoelastic nor recoverable, since (unlike polymer chains) metals do not have entanglements. Furthermore, creep is significant only at very high temperatures in metals. 

Our discussion of the viscoelastic properties of polymers is restricted to the linear viscoelastic behavior of solid polymers. The term linear refers to the mechanical response in whieh the ratio of the overall stress to strain is a function of time only and is independent of the magnitudes of the stress or strain (i.e., independent of stress or strain history). At the onset we concede that linear viscoelastie behavior is observed with polymers only under limited conditions involving homogeneous, isotropie, amorphous samples under small strains and at temperatures close to or above the Tg. In addition, test conditions must preclude those that ean result in specimen rupture. Nevertheless, the theory of linear viseoelastieity, in spite of its limited use in predicting service performance of polymeric articles, provides a useful reference point for many applications. 

Linear viscoelasticity is valid only imder conditions where structural changes in the material do not induce strain-dependent modulus. This condition is fulfilled by amorphous polymers. On the other hand, the structural changes associated with the orientation of crystalline polymers and elastomers produce anisotropic mechanical properties. Such polymers, therefore, exhibit nonlinear viscoelastic behavior. 

Creep and Stress Relaxations As reviewed, viscoelasticity can be related to designing (Chapter 3). In general, this is tractable only if the mechanical behavior is linear, although methods for nonlinear behavior... 

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