Shear storage compliance

The compliance can be used instead of the modulus to quantify storage and loss behaviour in viscoelastic solids. The shear storage compliance is defmed as ... 

Shear storage compliance Shear creep compliance Shear creep compliance Shear loss compliance Complex shear compliance... 

Figure 10. Complex shear storage compliance of Galcit I as a function of reduced frequency. Tq=30 C.

When the stress is decomposed into two components the ratio of the in-phase stress to the strain amplitude (j/a, maximum strain) is called the storage modulus. This quantity is labeled G (co) in a shear deformation experiment. The ratio of the out-of-phase stress to the strain amplitude is the loss modulus G"(co). Alternatively, if the strain vector is resolved into its components, the ratio of the in-phase strain to the stress amplitude t is the storage compliance J (m), and the ratio of ihe out-of-phase strain to the stress amplitude is the loss compliance J"(wi). G (co) and J ((x>) are associated with the periodic storage and complete release of energy in the sinusoidal deformation process. Tlie loss parameters G" w) and y"(to) on the other hand reflect the nonrecoverable use of applied mechanical energy to cause flow in the specimen. At a specified frequency and temperature, the dynamic response of a polymer can be summarized by any one of the following pairs of parameters G (x>) and G" (x>), J (vd) and or Ta/yb (the absolute modulus G ) and... 

The zero-shear viscoelastic properties of concentrated polymer solutions or polymer melts are typically defined by two parameters the zero-shear viscosity (f]o) and the zero-shear recovery compliance (/ ). The former is a measure of the dissipation of energy, while the latter is a measure of energy storage. For model polymers, the infiuence of branching is best established for the zero-shear viscosity. When the branch length is short or the concentration of polymer is low (i.e., for solution rheology), it is found that the zero-shear viscosity of the branched polymer is lower than that of the linear. This has been attributed to the smaller mean-square radius of the branched chains and has led to the following relation... 

The storage and loss shear moduli, G and G", vs. oscillation frequency ta, and the creep compliance J vs. time t, measured at each concentration and tanperature, were temperature shifted with respect to frequency or time. These temperature master curves at each concentration were then shifted to overlap one another along the frequency or time axis. The dynamic shear moduli master curves as a function of reduced frequency (oa ac are shown in fig. 4.4, and the shear creep compliance master curves as a function of reduced time tlajUc are shown in fig. 4.5. Master curves... 

Other types of linear viscoelastic experiments may be used. Dynamic shear compliance measurements provide the storage and loss compliances J (co) and J"(co). An equation analogous to Eq.(3.12) is available for determining the initial modulus from J"(co) ... 

The linear viscoelastic properties of all samples were characterized by dynamic shear measurements in the parallel-plate geometry. Experimental details have been previously published [9]. Using time-temperature equivalence, master curves for the storage and loss moduli were obtained. Fig. 1 shows the master curves at 140°C for the relaxation spectra and Table 3 gives the values of zero-shear viscosities, steady-state compliances and weight-average relaxation times at the same temperature. 

Although creep-compliance (Kawabata, 1977 Dahme, 1985) and stress-relaxation techniques (Comby et al., 1986) have been used to study the viscoelestic properties of pectin solutions and gels, the most common technique is small-deformation dynamic measurement, in which the sample is subjected to a low-amplitude, sinusoidal shear deformation. The resultant stress response may be resolved into an in-phase and 90° out-of-phase components the ratio of these stress components to applied strain gives the storage and loss moduli (G and G"), which can be related by the following expression ... 

Basically, a constant stress cr is applied on the system and the compliance J(Pa ) is plotted as a function of time (see Chapter 20). These experiments are repeated several times, increasing the stress in small increments from the smallest possible value that can be applied by the instrament). A set of creep curves is produced at various applied stresses, and from the slope of the linear portion of the creep curve (when the system has reached steady state) the viscosity at each applied stress, //, can be calculated. A plot of versus cr allows the limiting (or zero shear) viscosity /(o) and the critical stress cr (which may be identified with the true yield stress of the system) to be obtained (see also Chapter 4). The values of //(o) and <7 may be used to assess the flocculation of the dispersion on storage. 

Fig. 5.4 In a model with a single relaxation time, r, = 10 s, relaxed ereep eompliance /r = 1.0 GPa and unrelaxed shear modulus = 1.0 GPa, the changes in the creep compliance, from unrelaxed, /u, to relaxed, Jr, and corresponding changes in storage modulus (t) from relaxed, r, to unrelaxed, /lu, with increasing angular frequency co are shown, as are also associated changes in the loss compliance J"(t) and loss modulus, (after McCrum et al. (1967), with modification).

A fundamental quantity relating the basic viscoelastic functions (i.e., storage, loss modulus and compliance, shear viscosity) is the monomeric friction coefficient, which is a measure of the frictional resistence per monomer unit encountered by a moving chain segment. This co-... 

As an example of bulk viscoelastic behavior, data for a poly(vinyl acetate) of moderately high molecular weight are shown in Fig. 2-9. Measurements by McKinney and Belcher of the storage and loss bulk compliance B and B" at various temperatures and pressures are plotted after reduction to a reference temperature and pressure of 50°C and 1 atm respectively (see Chapter 11). The complex bulk compliance is formally analogous to the complex shear compliance, but the two functions present several marked contrasts. 

FIG. 10-7. Storage and loss shear compliances, normalized by the equilibrium compliance, plotted logarithmically against frequency for various network theories. (A) Mooney-Rouse theory, corresponding to Fig. 10-5 (B) Blizard model with trifurcate branching corresponding to tetrafunctional connectivity (C) tetrafunctional model of Chompff and Duiser ( >) Mooney-Rouse theory with most probable distribution of strand lengths. 

The inclusion of values in Table 1 l-III derived from dynamic bulk viscoelastic measurements implies the concept that the relaxation times describing time-de-pendent volume changes also depend on the fractional free volume—consistent with the picture of the glass transition outlined in Section C. In fact, the measurements of dynamic storage and loss bulk compliance of poly(vinyl acetate) shown in Fig. 2-9 are reduced from data at different temperatures and pressures using shift factors calculated from free volume parameters obtained from shear measurements, so it may be concluded that the local molecular motions needed to accomplish volume collapse depend on the magnitude of the free volume in the same manner as the motions which accomplish shear displacements. Moreover, it was pointed out in connection with Fig. 11 -7 that the isothermal contraction following a quench to a temperature near or below Tg has a temperature dependence which can be described by reduced variables with shift factors ay identical with those for shear viscoelastic behavior. These features will be discussed more fully in Chapter 18. 

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