8.

TIME AND FREQUENCY EFFECTS ON RELAXATION PROCESSES

377

Table 8.6 Multiple transitions in polystyrene and other amorphous polymers

Temperature 433 K (160C)

Transitions Tll

Polystyrene Mechanism Liquid1 to liquid2

General Mechanism Boundary between rubber elasticity and rubbery ow states Cooperative motion of several Kuhn segments, onset of reptation Single Kuhn segment motion Small-angle torsional vibrations, 23 mers Small-angle vibrations, single mer

373 K (100C)

Tg

325 K (50C) 130 K

b g

3848 K

Long-range chain motions, onset of reptation Torsional vibrations of phenyl groups Motion due to four carbon backbone moieties Oscillation or wagging of phenyl groups

behavior of spring and dashpot models (see Section 10.1). The critics contend that Tll is an instrumental artifact produced by the composite nature of the specimen in torsional braid analysis (TBA), since TBA instrumentation is the principal method of studying this phenomenon (see Figure 8.17). The Tll transition may be related to reptation. Many polymers show evidence of several transitions besides Tg. Table 8.6 summarizes the data for polystyrene, including the proposed molecular mechanisms for the several transitions. The General Mechanisms column in Table 8.6 follows the results described by Bershtein and Ergos (58) on a number of amorphous polymers. Clearly, different polymers may have somewhat different mechanistic details for the various transitions, especially the lower temperature ones. However, the participating moieties become smaller in size at lower temperatures. The onset of de Gennes reptation is probably associated with Tg, the motions being experimentally identied at Tg + 20C.

8.5 TIME AND FREQUENCY EFFECTS ON RELAXATION PROCESSES So far the discussion has implicitly assumed that the time (for static) or frequency (for dynamic) measurements of Tg were constant. In fact the observed glass transition temperature depends very much on the time allotted to the experiment, becoming lower as the experiment is carried out slower. For static or quasi-static experiments, the effect of time can be judged in two ways: (a) by speeding up the heating or cooling rate, as in dilatometric experiments, or (b) by allowing more time for the actual observation. For example, in measuring the shear modulus by Gehman instrumentation, the

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sample may be stressed for 100 s rather than 10 s before recording the angle of twist. In the case of dynamic experiments, especially where the sample is exposed to a sinusoidal motion, the frequency of the experiment can be varied over wide ranges. For dynamic mechanical spectroscopy, the frequency range can be broadened further by changing instrumentation. For example, DMS measurements in the 20,000-Hz range can best be carried out by employing sound waves. In dielectric studies, the frequency of the alternating electric eld can be varied. The inverse of changing the frequency of the experiment, making measurements as a function of time at constant temperature, is called stress relaxation or creep and is discussed in Section 8.5.2 and Chapter 10. In the following paragraphs a few examples of time and frequency effects are given. 8.5.1 Time Dependence in Dilatometric Studies It was pointed out in Section 8.3.1 that the elbow in volumetemperature studies constitutes a fundamental measure of the glass transition temperature, since the coefcient of expansion increases at Tg. The heating or cooling rate is important in determining exactly where the transition will be observed, however. As illustrated in Figure 8.18 (59), measuring the result twice after

Figure 8.18 Isochronous volumes of poly(vinyl acetate) at two times, 0.02 h and 100 h, after quenching to various isothermal temperatures (59). Also shown is the cubic coefcient of expansion, a, measured at the 0.02 h cooling rate.

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379

differing by a factor of 5000 reduces the glass transition temperature by about 8C. Similarly Tg varies with heating rate in DSC studies. 8.5.2 Time Dependence in Mechanical Relaxation Studies

If a polymer sample is held at constant strain and measurements of stress are recorded as a function of time, stress relaxation of the type shown in Figure 8.19 (60) will be observed. The shape of the curve shown in Figure 8.19 bears comparison with those in Figure 8.2. In the present case, log time has replaced temperature in the x axis, but the phenomenon is otherwise similar. As time is increased, more molecular motions occur, and the sample softens. It must be emphasized that the sample softens only after the time allowed for relaxation. For example, on a given curve of the type shown in Figure 8.19, the modulus might be 1 107 dynes/cm2 after 10 years, showing a rubbery behavior. Someone coming up and pressing his thumb into the material after 10 years will report the material as being much harder; however, it must be remembered that pressing ones thumb into a material is a short-time experiment, of the order of a few seconds. (This assumes physical relaxation phenomena only, not true chemical degradation.) The slope corresponding to the glass transition has been quantitatively treated by Aklonis and co-workers (6163) for relaxation phenomena. Aklonis dened a steepness index (SI) as the maximum of the negative slope of a stress relaxation curve in the glass transition region. They found that while

Figure 8.19 Master curve for polyisobutylene (60). The shift factor X, selected here so that log X298 = 0, is equivalent to the experimentally determined WLF At (see Section 8.6.1.2).

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Figure 8.20 The frequency dependence of the a and b transitions of polystyrene (42). Composite of both dynamic mechanical and dielectric studies of several researchers.

polyisobutylene has a SI of about 0.5, poly(methyl methacrylate) has a value of about 1.0, and polystyrene is close to 1.5. Aklonis treated the data theoretically, using the RouseBuecheZimm bead and spring model (6466), based in turn on the Debye damped torsional oscillator model (67,68). Aklonis concluded that values of SI equal to 0.5 represented a predominance of intramolecular forces and that a SI of 1.5 represented a predominance of intermolecular forces. A SI of 1.0 was an intermediate case. Stress relaxation is treated in greater detail in Chapter 10. 8.5.3 Frequency Effects in Dynamic Experiments The loss peaks such as those illustrated in Figure 8.7 and Figure 8.12 can be determined as a function of frequency. The peak frequency can then be plotted against 1/T to obtain apparent activation energies. Figure 8.20 (42) shows the a transition, Tg, of polystyrene increasing steadily in temperature as the frequency of measurement is increased. Both DMS and dielectric measurements are included. Since Tg is usually reported at 10 s (or 1 10-1 Hz), a glass transition temperature of 100C may be deduced from Figure 8.20, which is, in fact, the usually reported Tg.
The peaks in the loss spectrum are sometimes labeled a, b, g, . . . , with a being the highest temperature peak (Tg).

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THEORIES OF THE GLASS TRANSITION

381

The straight line for the a relaxation process, as drawn, corresponds to an apparent activation energy of 84 kcal/mol (69). The b relaxation possesses a corresponding apparent energy of activation of 35 kcal/mol. Section 8.6.2.3 discusses methods of calculating these values. As a rst approximation for many polymers, Tb @ 0.75Tg (70) at low frequencies. Bershtein et al. (71) point out that Tg and Tb frequently merge at a frequency of 106 to 108 Hz. The WLF equation (Section 8.6.1.2) says that Tg will change 6 to 7C per decade of frequency. Figure 8.19 yields about 5C change in Tg for a factor of 10 increase in the time scale, and Figure 8.20 yields about 7.5C per decade. Obviously this depends on the apparent energy of activation of the individual polymer, but many of the common carbon-backbone polymers have similar energies of activation. The effect of frequency on mechanical behavior is discussed further in Section 10.3. While each of these second-order transitions has a frequency dependence, the corresponding rst-order melting transition for semicrystalline polymers does not.

8.6 THEORIES OF THE GLASS TRANSITION The basic experimental behavior of polymers near their glass transition temperatures was explored in the preceding phenomenological description. In Section 8.5, Tg was shown to decrease steadily as the time allotted to the experiment was increased. One may raise the not so hypothetical question, is there an end to the decrease in Tg as the experiment is slowed? How can the transition be explained on a molecular level? These are the questions to which the theories of the glass transition are addressed. The following paragraphs describe three main groups of theories of the glass transition (14,72): free-volume theory, kinetic theory, and thermodynamic theory. Although these three theories may at rst appear to be as different as the proverbial three blind mens description of an elephant, they really examine three aspects of the same phenomenon and can be successfully unied, if only in a qualitative way.

8.6.1

The Free-Volume Theory

As rst developed by Eyring (73) and others, molecular motion in the bulk state depends on the presence of holes, or places where there are vacancies or voids (see Figure 8.21). When a molecule moves into a hole, the hole, of course, exchanges places with the molecule, as illustrated by the motion indicated in Figure 8.21. (This model is also exemplied in the childrens game involving a square with 15 movable numbers and one empty place; the object of the game is to rearrange the numbers in an orderly fashion.) With real materials, Figure 8.21 must be imagined in three dimensions.