Viscoelastic behavior, characterization

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 rheological properties of a fluid interface may be characterized by four parameters surface shear viscosity and elasticity, and surface dilational viscosity and elasticity. When polymer monolayers are present at such interfaces, viscoelastic behavior has been observed (1,2), but theoretical progress has been slow. The adsorption of amphiphilic polymers at the interface in liquid emulsions stabilizes the particles mainly through osmotic pressure developed upon close approach. This has become known as steric stabilization (3,4.5). In this paper, the dynamic behavior of amphiphilic, hydrophobically modified hydroxyethyl celluloses (HM-HEC), was studied. In previous studies HM-HEC s were found to greatly reduce liquid/liquid interfacial tensions even at very low polymer concentrations, and were extremely effective emulsifiers for organic liquids in water (6). 

Elastic behavior of liquids is characterized mainly by the ratio of first differences in normal stress, Ni, to the shear stress, t. This ratio, the Weissenberg number Wi = Nih, is usually represented as a function of the rate of shear y. Figure 7 depicts flow curves of some viscoelastic fluids, and Figure 8 presents a dimensionless standardized material function of these fluids. It again verifies that they behave similarly with respect to viscoelastic behavior under shear stress. 

As shown in Chapter 10, molecular dynamics in polymers is characterized by localised and cooperative motions that are responsible for the existence of different relaxations (a, (3, y). These, in turn, are responsible for energy dissipation, mechanical damping, mechanical transitions and, more generally, of what is called a viscoelastic behavior - intermediary between an elastic solid and a viscous liquid (Ferry, 1961 McCrum et al., 1967). 

Technological Advances. TMA and DMA are both widely employed in the characterization of viscoelastic behavior of polymers, composites, and other materials. Notably, TMA and DMA are particularly useful in identifying glass transitions and other low energy-associated sub-glass transitions, which may not be easily... 

Thixotropy is the tendency of certain substances to flow under external stimuli (e.g., mild vibrations). A more general property is viscoelasticity, a time-dependent transition from elastic to viscous behavior, characterized by a relaxation time. When the transition is confined to small regions within the bulk of a solid, the substance is said to creep. A substance which creeps is one that stretches at a time-dependent rate when subjected to constant stress and temperature. The approximately constant stretching rates at intermediate times are used to characterize the creeping characteristics of the material. 

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. 

The attenuation and velocity of acoustic energy in polymers are very different from those in other materials due to their unique viscoelastic properties. The use of ultrasonic techniques, such as acoustic spectroscopy, for the characterization of polymers has been demonstrated [47,48]. For AW devices, the propagation of an acoustic wave in a substrate causes an oscillating displacement of particles on the substrate surface. For a medium in intimate contact with the substrate, the horizontal component of this motion produces a shearing force. In such cases, there can be sufficient interaction between the acoustic wave and the adjacent medium to perturb the properties of the wave. For polymeric materials, attenuation and velocity of the acoustic wave will be affected by changes in the viscoelastic behavior of the polymer. 

A simple and flexible modeling scheme to quantitatively characterize complete viscoelastic properties of pol3nmers is readily useable with FTMA data. It contains the essential features of the frequency-temperature equivalence of the viscoelastic behaviors of pol3nmers and is easily adapted to modern computer systems. 

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. 

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... 

At high frequencies, the viscoelastic behavior of suspensions is primarily dissipative, as the particles are forced to move through the solvent much faster than they can relax by Brownian motion. The high-frequency behavior is characterized by a constant high-frequency viscosity = lim >oo G" jay, which has been subtracted from the data plotted in Fig. 

Wood-Adams, P. Dealy, J.M. deGroot, A.W. Redwine, O.D. Effect of molecular structure on the linear viscoelastic behavior of polyethylene. Macromolecules 2000, 33 (20), 7489-7499. Trinkle, S. Friedrich, C. Van Gurp-Palmen plot a way to characterize polydispersity of linear polymers. Rheol. Acta 2001, 40 (4), 322-328. Trinkle, S. Walter, P. Friedrich, C. Van Gurp-Palmen plot. II. Classification of long chain branched polymers by their topology. Rheol. Acta 2002, 41 (1-2), 103-113. 

For a crossllnked rubber sample, one simple parameter which can be used to roughly characterize the material is the crosslink density (v) or the average molecular weight between crosslinks (Mg a 1/v). It should be clear that this single parameter cannot completely represent a network in general. Nevertheless, it is well known that the viscoelastic behavior of a polymer network will vary with crosslink density as schematically depicted in Figure 1 for the creep behavior of a polymer at two crosslink densities < Vq. Here the kinetic theory of rubber elasticity... 

It is commonplace in pharmaceutical formulation to combine two or more polymers within a single dosage form, e.g., gel, semisolid, and solid oral dosage form as, in many instances, this ensures enhanced control of dosage form performance, e.g., stability, drug release rate, spreadability, etc. Once more, both the clinical and nonclinical performance of these systems may be related to their (complex) viscoelastic behavior, and, hence, these systems have been characterized using dynamic oscillatory methods. 

The practical interest of a lamellar liquid crystal lies in its suspending capability. A lyotropic liquid crystal exhibits a viscoelastic behavior that allows suspension of solid particles for a very long time. The lamellar phase is additionally characterized by an ideal critical strain to provide the suspension with good resistance to vibrations and convections, without impairing its flowability with too great a viscosity. 

One method that attempts to characterize the viscoelastic behavior is the force-deformation measurement. In this approach, a force point is applied... 

Viscoelasticity. Viscoelastic materials are characterized by a combination of elastic and viscous properties. Thus, the shear stress is not only dependent on the rate of shearing but on the strain 7 as well. In the simplest case, the viscoelastic behavior is governed by... 

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