Relaxation viscoelastic properties

In principle, the relaxation spectrum H(r) describes the distribution of relaxation times which characterizes a sample. If such a distribution function can be determined from one type of deformation experiment, it can be used to evaluate the modulus or compliance in experiments involving other modes of deformation. In this sense it embodies the key features of the viscoelastic response of a spectrum. Methods for finding a function H(r) which is compatible with experimental results are discussed in Ferry s Viscoelastic Properties of Polymers. In Sec. 3.12 we shall see how a molecular model for viscoelasticity can be used as a source of information concerning the relaxation spectrum. 

Tensile Testing. The most widely used instmment for measuring the viscoelastic properties of soHds is the tensile tester or stress—strain instmment, which extends a sample at constant rate and records the stress. Creep and stress—relaxation can also be measured. Numerous commercial instmments of various sizes and capacities are available. They vary greatiy in terms of automation, from manually operated to completely computer controlled. Some have temperature chambers, which allow measurements over a range of temperatures. Manufacturers include Instron, MTS, Tinius Olsen, Apphed Test Systems, Thwing-Albert, Shimadzu, GRC Instmments, SATEC Systems, Inc., and Monsanto. 

A typical stress—strain curve generated by a tensile tester is shown in Eigure 41. Creep and stress—relaxation results are essentially the same as those described above. Regarding stress—strain diagrams and from the standpoint of measuring viscoelastic properties, the early part of the curve, ie, the region... 

Lipatov, Y. S. Relaxation and Viscoelastic Properties of Heterogeneous Polymeric Compositions. Vol. 22, pp. 1-59. 

Although many different processes can control the observed swelling kinetics, in most cases the rate at which the network expands in response to the penetration of the solvent is rate-controlling. This response can be dominated by either diffu-sional or relaxational processes. The random Brownian motion of solvent molecules and polymer chains down their chemical potential gradients causes diffusion of the solvent into the polymer and simultaneous migration of the polymer chains into the solvent. This is a mutual diffusion process, involving motion of both the polymer chains and solvent. Thus the observed mutual diffusion coefficient for this process is a property of both the polymer and the solvent. The relaxational processes are related to the response of the polymer to the stresses imposed upon it by the invading solvent molecules. This relaxation rate can be related to the viscoelastic properties of the dry polymer and the plasticization efficiency of the solvent [128,129],... 

Distributions of relaxation or retardation times are useful and important both theoretically and practicably, because // can be calculated from /.. (and vice versa) and because from such distributions other types of viscoelastic properties can be calculated. For example, dynamic modulus data can be calculated from experimentally measured stress relaxation data via the resulting // spectrum, or H can be inverted to L, from which creep can be calculated. Alternatively, rather than going from one measured property function to the spectrum to a desired property function [e.g., Eft) — // In Schwarzl has presented a series of easy-to-use approximate equations, including estimated error limits, for converting from one property function to another (11). 

PTT has three dynamic mechanical viscoelastic relaxations [61, 62], a, (j and Y (Figure 11.9). The 70°C a-relaxation is the glass transition. In a study on the effect of methylene sequence length on aromatic polyester viscoelastic properties, Farrow et al. [63] reported a PTT a-relaxation as high as 95 °C. They also found that Tg of this series of aromatic polyesters did not show any odd-even effects, which was later confirmed by Smith et al. [64],... 

The dynamic mechanical thermal analyzer (DMTA) is an important tool for studying the structure-property relationships in polymer nanocomposites. DMTA essentially probes the relaxations in polymers, thereby providing a method to understand the mechanical behavior and the molecular structure of these materials under various conditions of stress and temperature. The dynamics of polymer chain relaxation or molecular mobility of polymer main chains and side chains is one of the factors that determine the viscoelastic properties of polymeric macromolecules. The temperature dependence of molecular mobility is characterized by different transitions in which a certain mode of chain motion occurs. A reduction of the tan 8 peak height, a shift of the peak position to higher temperatures, an extra hump or peak in the tan 8 curve above the glass transition temperature (Tg), and a relatively high value of the storage modulus often are reported in support of the dispersion process of the layered silicate. 

The effect of aging and of process variables on the rheological properties of solid proplnts has been the subject of mechanical shear relaxation spectroscopy (Ref 4). The technique is of interest to such filled polymer systems generally in that anisotropy in the viscoelastic properties can be readily observed... 

The linear viscoelastic properties are often expressed in terms of an auxiliary function, the relaxation time distribution, H(x) H(x)dlnx is the portion of the initial modulus contributed by processes with relaxation times in the range lnt, InT + dlnt ... 

Other viscoelastic properties also acquire new characteristics at high concentration. In undiluted systems the long time end of the relaxation time distribution remains approximately Rouse-like for chains with molecular weight below Mc, as suggested by the agreement with reduced Rouse moduli in Fig. 5.2. 

Chompff and Duiser (232) analyzed the viscoelastic properties of an entanglement network somewhat similar to that envisioned by Parry et al. Theirs is the only molecular theory which predicts a spectrum for the plateau as well as the transition and terminal regions. Earlier Duiser and Staverman (233) had examined a system of four identical Rouse chains, each fixed in space at one end and joined together at the other. They showed that the relaxation times of this system are the same as if two of the chains were fixed in space at both ends and the remaining two were joined to form a single chain with fixed ends of twice the original size. 

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