8.

4 OTHER TRANSITIONS AND RELAXATIONS

375

8.4

OTHER TRANSITIONS AND RELAXATIONS

As the temperature of a polymer is lowered continuously, the sample may exhibit several second-order transitions. By custom, the glass transition is designated the a transition, and successively lower temperature transitions are called the b, g, . . . transitions. One important second-order transition appears above Tg, designated the Tll (liquidliquid) transition. Of course, if the polymer is semicrystalline, it will also melt at a temperature above Tg. 8.4.1 The Schatzki Crankshaft Mechanism

8.4.1.1 Main-Chain Motions There appear to be two major mechanisms for transitions in the glassy state (45). For main-chain motions in hydrocarbon-based polymers such as polyethylene, the Schatzki crankshaft mechanism (46), Figure 8.16 (47), is thought to play an important role. Schatzki showed that eight CH2 units could be lined up so that the 12 bonds and the 78 bonds form a collinear axis. Then, given sufcient free volume, the intervening four CH2 units rotate more or less independently in the manner of an old-time automobile crankshaft. It is thought that at least four CH2 units in succession are required for this motion. The transition of polyethylene occurring near -120C is thought to involve the Schatzki mechanism. It is interesting to consider the basic motions possible for small hydrocarbon molecules by way of comparison. At very low temperatures, the CH3 groups in ethane can only vibrate relative to the other. At about 90 K ethane undergoes a second-order transition as detected by NMR absorption (48), and the two CH3 units begin to rotate freely, relative to one another. For propane and larger molecules, the number of motions becomes more complex (49), as now three-dimensional rotations come into play. One might imagine that noctane itself might have the motion illustrated in Figure 8.16 as one of its basic energy absorbing modes. 8.4.1.2 Side-Chain Motions The above considers main-chain motions. Many polymers have considerable side-chain foliage, and these groups can, of course, have their own motions. A major difference between main-chain and side-chain motions is the toughness imparted to the polymer. Low-temperature main-chain motions act

Figure 8.16 Schatzkis crankshaft motion (41) requires at least four CH2 groups in succession. As illustrated, for eight CH2 groups, bonds 1 and 7 are collinear and intervening CH2 units can rotate in the manner of a crankshaft (44).

376

GLASSRUBBER TRANSITION BEHAVIOR

to absorb energy much better than the equivalent side-chain motions, in the face of impact blows. When the main-chain motions absorb energy under these conditions, they tend to prevent main-chain rupture. (The temperature of the transition actually appears at or below ambient temperature, noting the equivalent frequency of the growing crack. The frequency dependence is discussed in Section 8.5.) Toughness and fracture in polymers are discussed in Chapter 11. 8.4.2 The Tll Transition

As illustrated in Figure 8.17 (50), the Tll transition occurs above the glass transition and is thought to represent the onset of the ability of the entire polymer molecule to move as a unit (9,51,52). Above Tll, physical entanglements play a much smaller role, as the molecule becomes able to translate as a whole unit. Although there is much evidence supporting the existence of a Tll (5153), it is surrounded by much controversy (5457). Reasons include the strong dependence of Tll on molecular weight and an analysis of the equivalent

Figure 8.17 Thermomechanical spectra (relative rigidity and logarithmic decrement versus temperature (K) of anionic polystyrene, Mn = 20,200 (50).

8.5

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