Viscoelastic behavior relaxation time

A parameter indicating whether viscoelastic effects are important is the Deborah number, which is the ratio of the characteristic relaxation time of the fluid to the characteristic time scale of the flow. For small Deborah numbers, the relaxation is fast compared to the characteristic time of the flow, and the fluid behavior is purely viscous. For veiy large Deborah numbers, the behavior closely resembles that of an elastic solid. 

The typical viscoelastic response, as shown in Fig. 2.18, is the propagation of a shock due to the compression, followed by a relaxation to an equilibrium state. The relaxation response is a significant part of the total response. Relaxation times are typically in the 0.1 /is regime. At pressures over about 2 GPa, PMMA shows a change in relaxation time which may be indicative of mechanical failure. Anderson has recently extended this work to other polymers and found similar strong viscoelastic behavior [92A01]. 

When a viscoelastic material is subjected to a constant strain, the stress initially induced within it decays in a time-dependent manner. This behavior is called stress relaxation. The viscoelastic stress relaxation behavior is typical of many TPs. The material specimen is a system to which a strain-versus-time profile is applied as input and from which a stress-versus-time profile is obtained as an output. Initially the material is subjected to a constant strain that is maintained for a long period of time. An immediate initial stress gradually approaches zero as time passes. The material responds with an immediate initial stress that decreases with time. When the applied strain is removed, the material responds with an immediate decrease in stress that may result in a change from tensile to compressive stress. The residual stress then gradually approaches zero. 

Viscoelastic stress-relaxation data are usually presented in one of two ways. In the first, the stress manifested as a function of time. Families of such curves may be presented at each temperature of interest. Each curve representing the stress-relaxation behavior of the material at a different level of... 

Some information concerning the intramolecular relaxation of the hyperbranched polymers can be obtained from an analysis of the viscoelastic characteristics within the range between the segmental and the terminal relaxation times. In contrast to the behavior of melts with linear chains, in the case of hyperbranched polymers, the range between the distinguished local and terminal relaxations can be characterized by the values of G and G" changing nearly in parallel and by the viscosity variation having a frequency with a considerably different exponent 0. This can be considered as an indication of the extremely broad spectrum of internal relaxations in these macromolecules. To illustrate this effect, the frequency dependences of the complex viscosities for both linear... 

Contrary to the phase separation curve, the sol/gel transition is very sensitive to the temperature more cations are required to get a gel phase when the temperature increases and thus the extension of the gel phase decreases [8]. The sol/gel transition as determined above is well reproducible but overestimates the real amount of cation at the transition. Gelation is a transition from liquid to solid during which the polymeric systems suffers dramatic modifications on their macroscopic viscoelastic behavior. The whole phenomenon can be thus followed by the evolution of the mechanical properties through dynamic experiments. The behaviour of the complex shear modulus G (o)) reflects the distribution of the relaxation time of the growing clusters. At the gel point the broad distribution of... 

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)... 

Most pigmented systems are considered viscoelastic. At low shear rates and slow deformation, these systems are largely viscous. As the rate of deformation or shear rate increases, however, the viscous response cannot keep up, and the elasticity of the material increases. There is a certain amount of emphasis on viscoelastic behavior in connection with pigment dispersion as well as ink transportation and transformation processes in high-speed printing machines (see below). Under periodic strain, a viscoelastic material will behave as an elastic solid if the time scale of the experiment approaches the time required for the system to respond, i.e., the relaxation time. Elastic response can be visualized as a failure of the material to flow quickly enough to keep up with extremely short and fast stress/strain periods. 

A unified approach to the glass transition, viscoelastic response and yield behavior of crosslinking systems is presented by extending our statistical mechanical theory of physical aging. We have (1) explained the transition of a WLF dependence to an Arrhenius temperature dependence of the relaxation time in the vicinity of Tg, (2) derived the empirical Nielson equation for Tg, and (3) determined the Chasset and Thirion exponent (m) as a function of cross-link density instead of as a constant reported by others. In addition, the effect of crosslinks on yield stress is analyzed and compared with other kinetic effects — physical aging and strain rate. 

Fluids that show elasticity to some extent are termed viscoelastic fluids, and some polymer solutions demonstrate such behavior. Elasticity is the tendency of a substance or body to return to its original form, after the applied stress that caused strain (i.e., a relative volumetric change in the case of a polymer solution) has been removed. The elastic modulus (Pa) is the ratio of the applied stress (Pa) to strain (-). The relaxation time (s) of a viscoelastic fluid is defined as the ratio of its viscosity (Pa s) to its elastic modulus. 

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. 

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. 

The effects of coupling of the DTO and RB units in not only one- but also three-dimensional arrays are discussed below and molecular weight trends illustrated. A fundamental connection between relaxation times and normal mode frequencies, shown to hold in all dimensions, allows the rapid derivation of the common viscoelastic and dielectric response functions from a knowledge of the appropriate lattice vibration spectra. It is found that the time and frequency dispersion behavior is much sharper when the oscillator elements are established in three-dimensional quasi-lattices as in the case of organic glasses. 

In a stress relaxation test, a polymer test specimen is deformed by a fixed amount, eo, and the stress required to hold that amount of deformation is recorded over time. This test is very cumbersome to perform, so the design engineer and the material scientist have tended to ignore it. In fact, several years ago, the standard relaxation test ASTM D2991 was dropped by ASTM. Rheologists and scientists, however, have been consistently using the stress relaxation test to interpret the viscoelastic behavior of polymers. 

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. 

Figure 8.1. Diagram showing Maxwell mechanical model of viscoelastic behavior of connective tissues. In this model an elastic element (spring) with a stiffness Em is in series with a viscous element (dashpot) with viscosity T m. This model is used to represent time dependent relaxation of stress in a specimen bold of fixed length.

Frequently, a characteristic relaxation time, k, is used to describe viscoelastic behavior. It is a measure for the time needed to transform the reversibly-elastically stored energy into friction heat ... 

In an earlier section, we have shown that the viscoelastic behavior of homogeneous block copolymers can be treated by the modified Rouse-Bueche-Zimm model. In addition, the Time-Temperature Superposition Principle has also been found to be valid for these systems. However, if the block copolymer shows microphase separation, these conclusions no longer apply. The basic tenet of the Time-Temperature Superposition Principle is valid only if all of the relaxation mechanisms are affected by temperature in the same manner. Materials obeying this Principle are said to be thermorheologically simple. In other words, relaxation times at one temperature are related to the corresponding relaxation times at a reference temperature by a constant ratio (the shift factor). For... 

These relaxation time equations together with Eqs. (2), (15), and (19) can be utilized in analyzing the experimental measurements of volume relaxation and recovery, of linear and nonlinear viscoelastic relaxations, and of yield behavior and stress-strain relationships. 

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