Viscoelastic behavior viscoelasticity

The drastic changes in the physical properties of polymers, due to reinforcement, also lead to pronounced changes in their viscoelastic behavior. Viscoelastic properties and relaxation behavior of composites change as a result of the formation of surface layers at the pol5Tner-solid interface. The molecular mobility of polymeric chains is restricted in these layers, which affects mechanical properties. 

A computer program was written to perform all the calculation. It is found that the three-element viscoelastic model provides reasonable estimation of the behavior of the polyvinyl chloride material during the impact... 

In this chapter we examine the elastic behavior of polymers. We shall see that this behavior is quite different from the elasticity displayed by metals and substances composed of small molecules. This is a direct consequence of the chain structure of the polymer molecules. In many polymers elasticity does not occur alone, but coupled with viscous phenomena. The combination of these effects is called viscoelasticity. We shall examine this behavior as well. 

Our objectives in this section are twofold to describe and analyze a mechanical model for a viscoelastic material, and to describe and interpret an experimental procedure used to study polymer samples. We shall begin with the model and then proceed to relate the two. Pay attention to the difference between the model and the actual observed behavior. 

A variety of commercial instruments are available for the determination of the viscoelastic behavior of samples. Figure 3.15 shows one such apparatus, the Rheovibron Viscoelastometer. This instrument also takes advantage of the complementarity that exists between time and temperature It operates at four frequencies over a 175°C temperature range. With accessories, both the frequency range and the temperature range can be broadened still further. 

We have relied heavily on the use of models in discussing the viscoelastic behavior of polymers in the transient and dynamic experiments of the last few sections. The models were mechanical, however, and while they provide a way for understanding the phenomena involved, they do not explicitly relate these phenomena to molecular characteristics. To establish this connection is the objective of this section. 

Through the dashpot a viscous contribution was present in both the Maxwell and Voigt models and is essential to the entire picture of viscoelasticity. These have been the viscosities of mechanical units which produce equivalent behavior to that shown by polymers. While they help us understand and describe observed behavior, they do not give us the actual viscosity of the material itself. 

In other work, the impact of thermal processing on linewidth variation was examined and interpreted in terms of how the resist s varying viscoelastic properties influence acid diffusion (105). The authors observed two distinct behaviors, above and below the resist film s glass transition. For example, a plot of the rate of deprotection as a function of post-exposure processing temperature show a change in slope very close to the T of the resist. Process latitude was improved and linewidth variation was naininiized when the temperature of post-exposure processing was below the film s T. 

These normal stresses are more pronounced for polymers with a very broad molecular weight distribution. Viscosities and viscoelastic behavior decrease with increasing temperature. In some cases a marked viscosity decrease with time is observed in solutions stored at constant temperature and 2ero shear. The decrease may be due to changes in polymer conformation. The rheological behavior of pure polyacrylamides over wide concentration ranges has been reviewed (5). 

Much more information can be obtained by examining the mechanical properties of a viscoelastic material over an extensive temperature range. A convenient nondestmctive method is the measurement of torsional modulus. A number of instmments are available (13—18). More details on use and interpretation of these measurements may be found in references 8 and 19—25. An increase in modulus value means an increase in polymer hardness or stiffness. The various regions of elastic behavior are shown in Figure 1. Curve A of Figure 1 is that of a soft polymer, curve B of a hard polymer. To a close approximation both are transpositions of each other on the temperature scale. A copolymer curve would fall between those of the homopolymers, with the displacement depending on the amount of hard monomer in the copolymer (26—28). 

The resistance to plastic flow can be schematically illustrated by dashpots with characteristic viscosities. The resistance to deformations within the elastic regions can be characterized by elastic springs and spring force constants. In real fibers, in contrast to ideal fibers, the mechanical behavior is best characterized by simultaneous elastic and plastic deformations. Materials that undergo simultaneous elastic and plastic effects are said to be viscoelastic. Several models describing viscoelasticity in terms of springs and dashpots in various series and parallel combinations have been proposed. The concepts of elasticity, plasticity, and viscoelasticity have been the subjects of several excellent reviews (21,22). 

The elongation of a stretched fiber is best described as a combination of instantaneous extension and a time-dependent extension or creep. This viscoelastic behavior is common to many textile fibers, including acetate. Conversely, recovery of viscoelastic fibers is typically described as a combination of immediate elastic recovery, delayed recovery, and permanent set or secondary creep. The permanent set is the residual extension that is not recoverable. These three components of recovery for acetate are given in Table 1 (4). The elastic recovery of acetate fibers alone and in blends has also been reported (5). In textile processing strains of more than 10% are avoided in order to produce a fabric of acceptable dimensional or shape stabiUty. 

For some materials the linear constitutive relation of Newtonian fluids is not accurate. Either stress depends on strain in a more complex way, or variables other than the instantaneous rate of strain must be taken into account. Such fluids are known collectively as non-Newtonian. Many different types of behavior have been observed, ranging from fluids for which the viscosity in the Navier-Stokes equation is a simple function of the shear rate to the so-called viscoelastic fluids, for which the constitutive equation is so different that the normal stresses can cause the fluid to flow in a manner opposite to that predicted for a Newtonian fluid. 

Eracture mechanics concepts can also be appHed to fatigue crack growth under a constant static load, but in this case the material behavior is nonlinear and time-dependent (29,30). Slow, stable crack growth data can be presented in terms of the crack growth rate per unit of time against the appHed R or J, if the nonlinearity is not too great. Eor extensive nonlinearity a viscoelastic analysis can become very complex (11) and a number of schemes based on the time rate of change of/have been proposed (31,32). 

Telechelic Ionomers. Low molecular weight polymers terminated by acid groups have been treated with metal bases to give ionomers in which the cations can be considered as connecting links in the backbones (67—71). The viscoelastic behavior of concentrated solutions has been linked to the neutralizing cation. 

Viscous Hquids are classified based on their rheological behavior characterized by the relationship of shear stress with shear rate. Eor Newtonian Hquids, the viscosity represented by the ratio of shear stress to shear rate is independent of shear rate, whereas non-Newtonian Hquid viscosity changes with shear rate. Non-Newtonian Hquids are further divided into three categories time-independent, time-dependent, and viscoelastic. A detailed discussion of these rheologically complex Hquids is given elsewhere (see Rheological measurements). 

The mechanical properties of LDPE fall somewhere between rigid polymers such as polystyrene and limp or soft polymers such as polyvinyls. LDPE exhibits good toughness and pHabiUty over a moderately wide temperature range. It is a viscoelastic material that displays non-Newtonian flow behavior, and the polymer is ductile at temperatures well below 0°C. Table 1 fists typical properties. 

Deformation is the relative displacement of points of a body. It can be divided into two types flow and elasticity. Flow is irreversible deformation when the stress is removed, the material does not revert to its original form. This means that work is converted to heat. Elasticity is reversible deformation the deformed body recovers its original shape, and the appHed work is largely recoverable. Viscoelastic materials show both flow and elasticity. A good example is SiEy Putty, which bounces like a mbber ball when dropped, but slowly flows when allowed to stand. Viscoelastic materials provide special challenges in terms of modeling behavior and devising measurement techniques. 

Detailed treatments of the rheology of various dispersed systems are available (71—73), as are reviews of the viscous and elastic behavior of dispersions (74,75), of the flow properties of concentrated suspensions (75—82), and of viscoelastic properties (83—85). References are also available that deal with blood red ceU suspensions (69,70,86). 

Many investigators beheve that the Bingham model accounts best for observations of electrorheological behavior (116,118), but other models have also been proposed (116,119). There is considerable evidence that ER materials behave as linear viscoelastic fluids while under the influence of electric field (120) thus it appears that these materials maybe thought of as elastic Bingham fluids. 

Figure 16 (145). For an elastic material (Fig. 16a), the resulting strain is instantaneous and constant until the stress is removed, at which time the material recovers and the strain immediately drops back to 2ero. In the case of the viscous fluid (Fig. 16b), the strain increases linearly with time. When the load is removed, the strain does not recover but remains constant. Deformation is permanent. The response of the viscoelastic material (Fig. 16c) draws from both kinds of behavior. An initial instantaneous (elastic) strain is followed by a time-dependent strain. When the stress is removed, the initial strain recovery is elastic, but full recovery is delayed to longer times by the viscous component.

The significance of G G tan 5, Tj, and Tj is that they can be determined experimentally and used to characterize real materials. These parameters depend on frequency and temperature, and this dependence can be used to define behavior. For example, viscoelastic fluids are often characterized by log—log plots of one or more of these quantities vs the angular frequency CO, as shown in Figure 21, which illustrates the behavior of a polymer melt (149). 

Dyna.mic Viscometer. A dynamic viscometer is a special type of rotational viscometer used for characterising viscoelastic fluids. It measures elastic as weU as viscous behavior by determining the response to both steady-state and oscillatory shear. The geometry may be cone—plate, parallel plates, or concentric cylinders parallel plates have several advantages, as noted above. 

The Weissenberg Rheogoniometer (49) is a complex dynamic viscometer that can measure elastic behavior as well as viscosity. It was the first rheometer designed to measure both shear and normal stresses and can be used for complete characteri2ation of viscoelastic materials. Its capabiUties include measurement of steady-state rotational shear within a viscosity range of 10 — mPa-s at shear rates of, of normal forces (elastic... 

Viscoelastic Measurement. A number of methods measure the various quantities that describe viscoelastic behavior. Some requite expensive commercial rheometers, others depend on custom-made research instmments, and a few requite only simple devices. Even quaHtative observations can be useful in the case of polymer melts, paints, and resins, where elasticity may indicate an inferior batch or unusable formulation. Eor example, the extmsion sweU of a material from a syringe can be observed with a microscope. The Weissenberg effect is seen in the separation of a cone and plate during viscosity measurements or the climbing of a resin up the stirrer shaft during polymerization or mixing. 

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