Other Dynamic Viscoelastic Functions

As indicated in another section, the response to an isotropic pressure as a step function of time gives the bulk creep compliance B(t). However, the response to a sinusoidal pressure gives the complex bulk compliance  

The Poisson ratio, like the bulk, tensile, and shear creep compliance, is an increasing function of time because the lateral contraction cannot develop instantaneously in uniaxial tension but takes an infinite time to reach its ultimate value. In response to a sinusoidal uniaxial stretch, the complete Poison ratio is obtained  

In the same way, the response to a sinusoidal change of volume yields the complex bulk relaxation modulus. 

Finally, the complex tensile compliance, and the complete tensile 

It should be noted that tan5 , = tanS and tanSj = tanS.  

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The dynamic tests at small amplitude in parallel plates or cone-and-plate geometry are simple and reproducible. From the experimental values of storage and loss shear moduli, G and G", respectively, first the yield stress ought to be extracted and then the characteristic four material parameters in Eq. (2.13), rjo, r, mi, and m2, might be calculated. Next, knowing these parameters one may calculate the Gross frequency relaxation spectrum (see Eqs. (2.31) and (2.32)) and then other linear viscoelastic functions. 

Other dynamic tests are more pragmatic in application, as they form a means of quantitatively monitoring the viscoelasticity of a material as it changes in real time or as a function of temperature. This means that melting, crystallization, gelation, and curing can all be followed without the test itself affecting the results. 

Photophysical and photochemical processes in polymer solids are extremely important in that they relate directly to the functions of photoresists and other molecular functional devices. These processes are influenced significantly by the molecular structure of the polymer matrix and its motion. As already discussed in Section 2.1.3, the reactivity of functional groups in polymer solids changes markedly at the glass transition temperature (Tg) of the matrix. Their reactivity is also affected by the / transition temperature, Tp, which corresponds to the relaxation of local motion modes of the main chain and by Ty, the temperature corresponding to the onset of side chain rotation. These transition temperatures can be detected also by other experimental techniques, such as dynamic viscoelasticity measurements, dielectric dispersion, and NMR spectroscopy. The values obtained depend on the frequency of the measurement. Since photochemical and photophysical parameters are measures of the motion of a polymer chain, they provide means to estimate experimentally the values of Tp and Tr. In homogeneous solids, reactions are related to the free volume distribution. This important theoretical parameter can be discussed on the basis of photophysical processes. 

In the above discussion, six functions Go(w), d(w), G (w), G"(w), /(w), and J"(oj) have been defined in terms of an idealized dynamic testing, while earlier we defined shear stress relaxation modulus G t) (see Equation 3.19) and shear creep compliance J(t) (see Equation 3.21) in terms of an idealized stress relaxation experiment and an idealized creep test, respectively. Mathematical relationships relating any one of these eight functions to any other can be derived. Such relationships for interconversion of viscoelastic function are described by Ferry [5], and interested readers are referred to this treatise for the same. 

The time-temperature superposition principle is valid for other dynamic or static viscoelastic functions as follows ... 

Mechanical testing procedures in common use involve other patterns of stress history than the simple creep and relaxation experiments on which the definitions of the transient viscoelastic functions are based, and the sinusoidally varying stress which is inherent in the definitions of the so-called dynamic properties. Certain relations between the behavior under coniplicated conditions and the basic viscoelastic functions are presented here together with some related problems. They are limited to linear viscoelastic systems and hence small strains, but in some cases could be extended to describe larger deformations, especially for simple extension. 

Further, it is shown how the unification technique can be extended to other rheological material functions, such as normal stress difference, dynamic viscoelastic parameters, and extensional viscosity, to obtain coalesced curves which are grade and temperature invariant. 

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). 

Several material properties exhibit a distinct change over the range of Tg. These properties can be classified into three major categories—thermodynamic quantities (i.e., enthalpy, heat capacity, volume, and thermal expansion coefficient), molecular dynamics quantities (i.e., rotational and translational mobility), and physicochemical properties (i.e., viscosity, viscoelastic proprieties, dielectric constant). Figure 34 schematically illustrates changes in selected material properties (free volume, thermal expansion coefficient, enthalpy, heat capacity, viscosity, and dielectric constant) as functions of temperature over the range of Tg. A number of analytical methods can be used to monitor these and other property changes and... 

The viscoelastic response of polymer melts, that is, Eq. 3.1-19 or 3.1-20, become nonlinear beyond a level of strain y0, specific to their macromolecular structure and the temperature used. Beyond this strain limit of linear viscoelastic response, if, if, and rj become functions of the applied strain. In other words, although the applied deformations are cyclic, large amplitudes take the macromolecular, coiled, and entangled structure far away from equilibrium. In the linear viscoelastic range, on the other hand, the frequency (and temperature) dependence of if, rf, and rj is indicative of the specific macromolecular structure, responding to only small perturbations away from equilibrium. Thus, these dynamic rheological properties, as well as the commonly used dynamic moduli... 

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. 

Dynamic mechanical tests have been widely applied in the viscoelastic analysis of polymers and other materials. The reason for this has been the technical simplicity of the method and the low tensions and deformations used. The response of materials to dynamic perturbation fields provides information concerning the moduli and the compliances for storage and loss. Dynamic properties are of considerable interest when they are analyzed as a function of both frequency and temperature. They permit the evaluation of the energy dissipated per cycle and also provide information concerning the structure of the material, phase transitions, chemical reactions, and other technical properties, such as fatigue or the resistance to impact. Of particular relevance are the applications in the field of the isolation of vibrations in mechanical engineering. The dynamic measurements are a... 

LDPE, and with polypropylene, PP, was studied In steady state shear, dynamic shear and uniaxial extenslonal fields. Interrelations between diverse rheological functions are discussed In terms of the linear viscoelastic behavior and Its modification by phase separation Into complex morphology. One of the more Important observations Is the difference In elongational flow behavior of LLDPE/PP blends from that of the other blends the strain hardening (Important for e.g. fllm blowing and wire coating) occurs In the latter ones but not In the former. 

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