Relaxation time maximum

The time-temperature superpositioning principle was applied f to the maximum in dielectric loss factors measured on poly(vinyl acetate). Data collected at different temperatures were shifted to match at Tg = 28 C. The shift factors for the frequency (in hertz) at the maximum were found to obey the WLF equation in the following form log co + 6.9 = [ 19.6(T -28)]/[42 (T - 28)]. Estimate the fractional free volume at Tg and a. for the free volume from these data. Recalling from Chap. 3 that the loss factor for the mechanical properties occurs at cor = 1, estimate the relaxation time for poly(vinyl acetate) at 40 and 28.5 C. 

Stopping distance The maximum distance a moving particle will travel in still air after all the external forces are removed. In the Stokes region it is the velocity of the particle times the relaxation time. 

The rheological parameter variations with blend compositions are shown in Figs. 4,5 and 6. The variation of relaxation time (Fig. 4) seems to show an increasing pattern up to 40% of NBR, then there is a sharp decrease until 60% of NBR, and finally there is a further increase of relaxation time in the preblends. Preheating of blends, however, results in a longer relaxation time than in the preblends and a maximum at 50 50 ratio at all shear rates. 

Earlier studies [14,15] clearly reveal that there is a reaction between two polymers and that the extent of reaction depends on the blend ratio. As 50 50 ratio has been found to the optimum (from rheological and infrared studies) ratio for interchain crosslinking, the higher heat of reaction for the NBR-rich blend may be attributed to the cyclization of NBR at higher temperatures. There is an inflection point at 50 50 ratio where maximum interchain crosslinking is expected. Higher viscosity, relaxation time, and stored elastic energy are observed in the preheated blends. A maximum 50-60% of Hypalon in NBR is supposed to be an optimum ratio so far as processibility is concerned. 

The plot of the rheological parameters (relaxation time, shear modulus, and stored elastic energy) are shown in Figs. 22-24. The relaxation time increases as the ACM content is increased to attain a maximum at 60 40 = ACM XNBR blend ratio for the preblends. For lower shear rate the rise is sharp and after 60 40 blend ratio, // remains almost constant, whereas for the higher shear rate region the rise is not sharp and after 60 40 blend ratio ty decreases as ACM percent increased in the blend. In the case of the preheated blends the /y increases up to 50 50 blend ratio and then decreases with the addition of ACM in the blend. The preheating increases the ty in both shear rate regions. 

Equation (3) is plotted with two different time scales in Figures 1 and 2 for values somewhat typical of an elastomer. All the initial deformation takes place in the spring at a later time the dashpot starts to relax and allows the spring to contract. Most of the relaxation takes place within one decade of time on both sides of the relaxation time, but this is shown clearly only in Figure 2. On the logarithmic time scale, the stress-relaxation curve has a maximum slope at the time / = T and the stress ratio cr/cr is 0.3679 ore. The stress relaxation may also be given in terms of a stress-relaxation modulus Er(t) ... 

The other mechanism responsible for unstable spinning is the mechanical resistance of a viscoelastic material to rapid deformation. It is a well-known fact that increased yam breaks can be a consequence of spinning speed, which relates to prolonged relaxation time and therefore to break. The fracture can be observed at a maximum extent of deformation under distortion of the covalent bonds. 

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