Superposition modulus

It is apparent therefore that the Superposition Principle is a convenient method of analysing complex stress systems. However, it should not be forgotten that the principle is based on the assumption of linear viscoelasticity which is quite inapplicable at the higher stress levels and the accuracy of the predictions will reflect the accuracy with which the equation for modulus (equation (2.33)) fits the experimental creep data for the material. In Examples (2.13) and (2.14) a simple equation for modulus was selected in order to illustrate the method of solution. More accurate predictions could have been made if the modulus equation for the combined Maxwell/Kelvin model or the Standard Linear Solid had been used. 

If creep curves are available at only one temperature then the situation is a little more difficult. It is known that properties such as modulus will decrease with temperature, but by how much Fortunately it is possible to use a time-temperature superposition approach as follows ... 

A plastic with a time dependent creep modulus as in the previous example is stressed at a linear rate to 40 MN/m in 100 seconds. At this time the stress in reduced to 30 MN/m and kept constant at this level. If the elastic and viscous components of the modulus are 3.5 GN/m and 50 x 10 Ns/m, use Boltzmann s Superposition Principle to calculate the strain after (a) 60 seconds and (b) 130 seconds. 

Object in this section is to review how rheological knowledge combined with laboratory data can be used to predict stresses developed in plastics undergoing strains at different rates and at different temperatures. The procedure of using laboratory experimental data for the prediction of mechanical behavior under a prescribed use condition involves two principles that are familiar to rheologists one is Boltzmann s superposition principle which enables one to utilize basic experimental data such as a stress relaxation modulus in predicting stresses under any strain history the other is the principle of reduced variables which by a temperature-log time shift allows the time scale of such a prediction to be extended substantially beyond the limits of the time scale of the original experiment. 

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 temperature-time superposition principle is illustrated in Figure 8 by a hypothetical polymer with a TK value of 0°C for the case of stress relaxation. First, experimental stress relaxation curves are obtained at a series of temperatures over as great a time period as is convenient, say from 1 min to 10 min (1 week) in (he example in Figure 8. In making the master curve from the experimental data, the stress relaxation modulus ,(0 must first be multiplied by a small temperature correction factor/(r). Above Tg this correction factor is where Ttrt is the chosen reference... 

If the Boltzmann superposition principle holds, the creep strain is directly proportional to the stress at any given time, f Similarly, the stress at any given lime is directly proportional to the strain in stress relaxation. That is. the creep compliance and the stress relaxation modulus arc independent of the stress and slrai . respectively. This is generally true for small stresses or strains, but the principle is not exact. If large loads are applied in creep experiments or large strains in stress relaxation, as can occur in practical structural applications, nonlinear effects come into play. One result is that the response (0 l,r relaxation times can also change, and so can ar... 

For glassy and crystalline polymers there are few data on the variation of stress relaxation with amplitude of deformation. However, the data do verily what one would expect on the basis of the response of elastomers. Although the stress-relaxation modulus at a given time may be independent of strain at small strains, at higher initial fixed strains the stress or the stress-relaxation modulus decreases faster than expected, and the lloltz-nuinn superposition principle no longer holds. 

Because of equipment limitations in measuring stress and strain in polymers, the time-temperature superposition principle is used to develop the viscoelastic response curve for real polymers. For example, the time-dependent stress relaxation modulus as a function of time and temperature for a PMMA resin is shown in... 

Fig. 3.14. The data is for a very broad range of times and temperatures. The superposition principle is based on the observation that time (rate of change of strain, or strain rate) is inversely proportional to the temperature effect in most polymers. That is, an equivalent viscoelastic response occurs at a high temperature and normal measurement times and at a lower temperature and longer times. The individual responses can be shifted using the WLF equation to produce a modulus-time master curve at a specified temperature, as shown in Fig. 3.15. The WLF equation is as shown by Eq. 3.31 for shifting the viscosity. The method works for semicrystalline polymers. It works for amorphous polymers at temperatures (T) greater than Tg + 100 °C. Shifting the stress relaxation modulus using the shift factor a, works in a similar manner.

Figure 3.15 Modulus-time master curve at 115°C based on time-temperature superposition of the PMMA resin data shown in Fig. 3.14 (Fig. 8.13 in Rodriguez [1]). The T for PMMA resin is 105°C...

The two waves—one , from the common source S the other, 0 from the generator of theta waves S —overlap at the detection region. The expected intensity at the array of detectors DR, after n arrivals of particles, is given by the squared modulus of the superposition of two waves at each instant of time, summed for all n arrivals ... 

In Eq. (4.13) NT is the total number of internal degrees of freedom per unit volume which relax by simple diffusion (NT — 3vN for dilute solutions), and t, is the relaxation time of the ith normal mode (/ = 1,2,3NT) for small disturbances. Equation (4.13), together with a stipulation that all relaxation times have the same temperature coefficient, provides, in fact, the molecular basis of time-temperature superposition in linear viscoelasticity. It also reduces to the expression for the equilibrium shear modulus in the kinetic theory of rubber elasticity when tj = oo for some of the modes. 

Fig. 5.8. Storage modulus vs frequency for narrow distribution polystyrene melts, reduced to 160° C by temperature-frequency superposition. Molecular weight range from Mw = 8900 (L9) to Mw= 581000 (L18) (124). [Reproduced from Macromolecules 3, 111 (1970).]...

Fig. Z4 (a) Temperature ramp at a frequency a> = lOrads (strain amplitude A = 2%) for a nearly symmetric PEP-PEE diblock with Mn = 8.1 X 104gmol l, heating from the lamellar phase into the disordered phase. The order-disorder transition occurs at 291 1 °C, the grey band indicates the experimental uncertainty on the ODT (Rosedale and Bates 1990). (b) Dynamic elastic shear modulus as a function of reduced frequency (here aT is the time-temperature superposition shift factor) for a nearly symmetric PEP-PEE diblock with Mn = 5.0 X 1O g mol A Shift factors were determined by concurrently superimposing G and G"for w > and w > " respectively. The filled and open symbols correspond to the ordered and disordered states respectively. The temperature dependence of G (m < oi c) for 96 < T/°C 135 derives from the effects of composition fluctuations in the disordered state (Rosedale and Bates 1990). (c) G vs. G"for a PS-PI diblock with /PS = 0.83 (forming a BCC phase) (O) 110°C (A) 115°C ( ) 120°C (V) 125°C ( ) 130°C (A) 135°C ( ) 140°C ( ) 145°C. The ODT occurs at about 130°C (Han et at. 1995).

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