Shear relaxation modulus determination

The beauty of the linear viscoelastic analysis lies in the fact that once a viscoelastic function is known, the rest of the functions can be determined. For example, if one measures the comphance function J t), the values of the components of the complex compliance function can in principle be determined from J(t) by using Fourier transforms [Eqs. (6.30)]. On the other hand, the components of the complex relaxation moduh can be obtained from those of / (co) by using Eq. (6.50). Even more, the real components of both the complex relaxation modulus and the complex compliance function can be determined from the respective imaginary components, and vice versa, by using the Kronig-Kramers relations. Moreover, the inverse of the Fourier transform of G (m) and/or G"(co) [/ (co) and/or /"(co)] allows the determination of the shear relaxation modulus (shear creep compliance). Finally, the convolution integrals of Eq. (5.57) allow the determination of J t) and G t) by an efficient method of numerical calculation outlined by Hopkins and Hamming (13). 

At the longest times associated with the shear-relaxation modulus, the disentanglement processes determine the value of fhe shear viscosity. It is observed experimentally that the shear viscosity depends on chain length as ... 

Step-strain stress-relaxation measurements have been frequently used to determine Sr(X) for polymer melts > . Equation (6) shows that if separability of time and strain effects is possible for the melt under consideration, the stress after a step elongational strain can be factored into a time-dependent function, the linear shear relaxation modulus G(t), and a strain-dependent function, the nonlinear strain measure Sr(X). Also other types of experiment may be oerformed to obtain Sr(X), such as constant-strain-rate experiments "", creep under constant stress and constant-stretching-rate experiments but these methods require more involved analytical and/or numerical calculations. 

This expression allows the determination of the viscosity at zero shear rate from the time dependence of the relaxation modulus. 

There are a great number of techniques for the experimental determination of viscoelastic functions. The techniques most frequently found in the literature are devoted to measuring the relaxation modulus, the creep compliance function, and the components of the complex modulus in either shear, elongational, or flexural mode (1-4). Although the relaxation modulus and creep compliance functions are defined in the time domain, whereas the complex viscoelastic functions are given in the frequency domain, it is possible, in principle, by using Fourier transform, to pass from the time domain to the frequency domain, or vice versa, as discussed earlier. 

The final experiment that may be of value in characterizing the flow characteristics of LCP is that of stress relaxation following a suddenly imposed shear strain. In this experiment various strain amplitudes are imposed very rapidly. In this way no flow occurs. At low strain levels intermolecular forces which can result in yield stresses may be more readily identified. From this type of experiment we determine the strain dependent relaxation modulus defined as follows ... 

Having discussed the microscopic dynamical properties of a system of Rouse-chains, we now inquire about the resulting mechanical behavior and consider as an example the shear stress relaxation modulus, G t). G t) can be determined with the aid of the fluctuation-dissipation theorem, utilizing Eq. (6.7)... 

The correspondence principle following the Boltzmann superposition principle allows the conversion of the common mechanical relationships of linear elasticity theory into linear viscoelasticity simply by replacing cr by time-dependent a t) and e by time-dependent e(t). Young s modulus E or the relaxation modulus Ej (f)= cr(f)/e is accordingly transformed to the creep modulus c(f) = cile t) orthe creep compliance/(f) = s(f)/(7,respectively. These time-dependent parameters can be determined from tensile creep and relaxation experiments. In compression or shear mode, the corresponding parameters of moduli are calculated in a similar manner. 

Thus, the aim of linear viscoelastic measurements (for incompressible materials) is to experimentally determine the relaxation modulus G(t) or quantities equivalent to G(t). In most cases of actual linear viscoelastic measurements, a sinusoidal shear strain y(t) =yosin(Bt (co is the angular frequency and is equal to 2rr/ with / being the frequency in the unit of Hertz) with the amplitude yo 1 is applied to a material. From eqn [22], the resulting shear stress is expressed as... 

Not only are the creep compliance and the stress relaxation shear modulus related but in turn the shear modulus is related to the tensile modulus which itself is related to the stress relaxation time 0. It is therefore in theory possible to predict creep-temperature relationships from WLF data although in practice these are still best determined by experiment. 

Rheological parameters, such as relaxation time, shear modulus, and stored elastic energy, are determined from the extrudate swell and stress-strain data as previously described. Representative examples of the variation of these parameters with blend ratios for both blends are shown in Figs. 16-18. Figure 16 shows that relaxation time for both preblends without heating and... 

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... 

In the case of dynamic mechanical relaxation the Zimm model leads to a specific frequency ( ) dependence of the storage [G ( )] and loss [G"(cd)] part of the intrinsic shear modulus [G ( )] [1]. The smallest relaxation rate l/xz [see Eq. (80)], which determines the position of the log G (oi) and log G"(o>) curves on the logarithmic -scale relates to 2Z(Q), if R3/xz is compared with Q(Q)/Q3. The experimental results from dilute PDMS and PS solutions under -conditions [113,114] fit perfectly to the theoretically predicted line shape of the components of the modulus. In addition l/xz is in complete agreement with the theoretical prediction based on the pre-averaged Oseen tensor. 

Measurement of the equilibrium properties near the LST is difficult because long relaxation times make it impossible to reach equilibrium flow conditions without disruption of the network structure. The fact that some of those properties diverge (e.g. zero-shear viscosity or equilibrium compliance) or equal zero (equilibrium modulus) complicates their determination even more. More promising are time-cure superposition techniques [15] which determine the exponents from the entire relaxation spectrum and not only from the diverging longest mode. 

The plateau modulus is determined by the region in which these two relaxation modes cross. The plateau modulus, the low shear viscosity and the tube disengagement time are given in Section 6.4.3 as... 

In addition to knowing the temperature shift factors, it is also necessary to know the actual value of ( t ) at some temperature. Dielectric relaxation studies often have the advantage that a frequency of maximum loss can be determined for both the primary and secondary process at the same temperature because e" can be measured over at least 10 decades. For PEMA there is not enough dielectric relaxation strength associated with the a process and the fi process has a maximum too near in frequency to accurately resolve both processes. Only a very broad peak is observed near Tg. Studies of the frequency dependence of the shear modulus in the rubbery state could be carried out, but there... 

In order to elucidate the correlation method it may be recalled that the viscosity 77 approaches asymptotically to the constant value r c with decreasing shear rate q. Similarly, the characteristic time t approaches a constant value xQ and the shear modulus G has a limiting value G0 at low shear rates. Bueche already proposed that the relationship between 77 and q be expressed in a dimensionless form by plotting 77/r]0 as a function of qx. According to Vinogradov, also the ratio t/tq is a function of qxQ. If the zero shear rate viscosity and first normal stress are determined, then a time constant x0 may be calculated with the aid of Eqs. (15.60). This time constant is sometimes used as relaxation time, in order to be able to produce general correlations between viscosity, shear modulus and recoverable shear strain as functions of shear rate. 

A variety of rheological tests can be used to evaluate the nature and properties of different network structures in foods. The strength of bonds in a fat crystal network can be evaluated by stress relaxation and by the decrease in elastic recovery in creep tests as a function of loading time (deMan et al. 1985). Van Kleef et al. (1978) have reported on the determination of the number of crosslinks in a protein gel from its mechanical and swelling properties. Oakenfull (1984) used shear modulus measurements to estimate the size and thermodynamic stability of junction zones in noncovalently cross-linked gels. 

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