Glass Transition frequency effects

The kinetic nature of the glass transition should be clear from the last chapter, where we first identified this transition by a change in the mechanical properties of a sample in very rapid deformations. In that chapter we concluded that molecular motion could simply not keep up with these high-frequency deformations. The complementarity between time and temperature enters the picture in this way. At lower temperatures the motion of molecules becomes more sluggish and equivalent effects on mechanical properties are produced by cooling as by frequency variations. We shall return to an examination of this time-temperature equivalency in Sec. 4.10. First, however, it will be profitable to consider the possibility of a thermodynamic description of the transition which occurs at Tg. 

When dipoles are directly attached to the chain their movement will obviously depend on the ability of chain segments to move. Thus the dipole polarisation effect will be much less below the glass transition temperature, than above it Figure 6.4). For this reason unplasticised PVC, poly(ethylene terephthalate) and the bis-phenol A polycarbonates are better high-frequency insulators at room temperature, which is below the glass temperature of each of these polymers, than would be expected in polymers of similar polarity but with the polar groups in the side chains. 

In the case of polymer molecules where the dipoles are not directly attached to the main chain, segmental movement of the chain is not essential for dipole polarisation and dipole movement is possible at temperatures below the glass transition temperature. Such materials are less effective as electrical insulators at temperatures in the glassy range. With many of these polymers, e.g., poly(methyl methacrylate), there are two or more maxima in the power factor-temperature curve for a given frequency. The presence of two such maxima is due to the different orientation times of the dipoles with and without associated segmental motion of the main chain. 

These analysers exist in many forms but are essentially relatively small bench instruments, which use small test pieces and can be programmed to measure damping and dynamic moduli as a function of temperature and frequency. Apart from their importance for measuring the dynamic properties where these are relevant to service, they allow the generation of a large quantity of data over ranges of temperature and frequency extremely efficiently. Hence, they can be used effectively to obtain modulus even if the application is not dynamic. Another valuable use is to obtain glass transition temperatures. 

Most spectroscopic techniques (e.g. infrared and Raman spectroscopy) provide a snapshot view of the structure of a liquid because the timescale of the techniques is of the order of lattice vibration. However, NMR can probe much lower frequency motions, motions which are important in the glass transition and the viscosity of a silicate liquid. In addition, the timescale of the NMR experiment may be varied (by changing the magnetic field, or the type of experiment, T or T fJ, or observing quadrupolar effects) from a few hertz to several hundred megahertz. 

Dielectric permittivity and loss for both polymers under study can be observed on Figs. 2.17 and 2.18. In both figures a prominent peak corresponding to the dynamic glass transition temperature can be observed, which at low frequencies is overlapped by conductivity effects. Moreover, in both polymers a broad secondary peak is observed at about -50°C. This peak is more prominent in P2tBCHM which is in good... 

Figures 2.37 and 2.38, show the isochronal curves of the permittivity and loss factor for P2NBM and P3M2NBM as a function of temperature at fixed frequencies. A prominent relaxation associated with the dynamic glass transition is observed in both polymers. Clearly the effect of the methyl substitution in position 3 of the norbornyl group is to decrease the temperature of this relaxational process.

Plastic Deformation Plastic deformation results from the combination of thermal and mechanical effects. The thermoplastic excipient was subjected to a temperature above its glass transition temperature (Tg) and to a high-frequency mechanical pressure that can avoid the elastic recovery of the material. 

Application of this method for miscibility studies of blends of ethylene-vinyl acetate copolymer (45 wt.- % Ac) with chlorinated polyethylene (52 wt.- % Cl) at a constant frequency of 37 Hz is demonstrated in Fig. 13. The method has shown single T s for the blends studied. The Maxwell-Winger-Sillars conductivity effect which appears after the glass transition temperatures is also shown in this Figure. 

The rabber modulus increases with an increasing volume fraction of Aerosil. The modulus increase can be caused by the elastomer-filler and filler-filler interactions and by an increase of effective filler content. A very sharp peak for the tanZ is observed at 163 K for an unfilled crosslinked sample. This maximum corresponds to the glass transition of the rubber. Furthermore, it is observed that the Tg of the rubber does not change in the presence of filler. However, the second maximum of to 5 can be seen in the vicinity of 200 K for filled samples. The intensity of this maximum becomes more pronounced with increasing Aerosil content. This observation is in agreement with the results of the h and Ty relaxation study, as demonstrated in Fig. 4a and 6, respectively. Therefore, it seems reasonable to assign the maximum for at 200 K to the motion of adsorbed chain units. This maximum is observed at a lower temperature than the H and T, minimum for the adsorbed chain units (at about 280 K) due to difference in frequency of these methods 1.6 Hz and 46-90 MHz, respectively. 

FIGURE 2.10 Effect of conditioning time on glass transition temperature, Eg, assigned as a temperature at the peak of the DMA loss modulus. Eg, measured at three different oscillating frequencies of 1, 10, and 100 Hz, is shown for the specimens with longitudinal and transverse groove orientations. 

High-frequency US has been used to assist crystallization around the glass transition temperature for metallic glass dramatic effect has been found which has been ascribed to rapid crystallization caused by a stochastic resonance in which the jump frequency of atoms matches the frequency of the interatomic potential change by the US vibration [143]. 

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