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posed the concept of a cooperatively rearranging region, dened as the smallest region capable of conformational change without a concomitant change outside the region. At T2 this region becomes equal to the size of the sample, since only one conformation is available. Adam and Gibbs rederived the WLF equation, putting it in terms of the potential energy hindering the cooperative rearrangement per mer, the molar conformational entropy, and the change in the heat capacity at Tg. By choosing the temperature T in the WLF equation to be Ts [see equation (8.49)] and suitable rearrangements of the WLF formulation to isolate T2, they found that Tg = 1.30 8.4% T2 (8.60)

for a wide range of glass-forming systems, both polymeric and low molecular weight. For low-temperature elastomers such as the polybutadiene family, Tg @ 200 K. According to equation (8.60), T2 @ 154 K, or about 50 K below Tg. According to the WLF equation, equation (8.48), the viscosity becomes innite at T - Tg = -51.6C, which is about the same number. Although this simplied approach yields less quantitative agreement at higher temperatures, the ideas still are interesting.

8.7 8.7.1


Studies of the increase in Tg with increasing polymer molecular weight date back to the works of Ueberreiter in the 1930s (105). The theoretical analysis of Fox and Flory (74) (see Section indicated that the general relationship between Tg at a molecular weight M was related to the glass temperature at innite molecular weight, Tg, by Tg = Tg K (a R - a G )M (8.61)

with K being a constant depending on the polymer. Equation (8.61) follows from the decrease in free volume with increasing molecular weight, caused in turn by the increasing number of connected mers in the system, and decreased number of end groups. The ubiquitous polystyrene seems to have been investigated more than any other polymer (74,105,106). DSC data, rst extrapolated to low heating rate, are shown in Figure 8.26 (99). (These data also show an endothermic peak at Tg; see earlier discussions.) The equation for slow heating rates may be expressed



Figure 8.26 The glass transition temperature of polystyrene as a function of 1/Mn (106).

Tg = 106C -

2.1 10 5 Mn


For heating rates normally encountered (74) Tg = 100 C 1.8 10 5 Mn (8.63)

The molecular weight in equation (8.63) is for fractionated polystrene. For slow experiments, these equations suggest a 6C increase in Tg at innite molecular weight. 8.7.2 Effect of Tg on Polymerization

According to equation (8.61) the glass transition depends on the molecular weight. What happens during an isothermal polymerization? When the polymerization begins, the monomers are always in the liquid state. Sometimes, however, the system may go through Tg and the polymer may vitrify as the reaction proceeds. Since molecular motion is much reduced when the system is below Tg, the reaction substantially stops. Two conditions can be distinguished. First, during a chain polymerization, the monomer effectively acts like a plasticizer for the nascent polymer. An example relates to the emulsion polymerization of polystyrene, often carried out at about 80C. The reaction will not proceed quite to 100% conversion, because the system vitries. Second, during stepwise polymerization, the molecular weight is continually increasing. An especially interesting case involves gelation. Taking epoxy polymerization as an example, the resin is simultaneously polymerizing and cross-linking (see Section 3.7.3). Gillham (107112) pointed out the need to postcure the polymer above Tg, the glass transition temperature of the fully cured system. He developed a timetemperaturetransformation (TTT) reaction diagram that may be used

Resin is an early term for polymer, often used with epoxies. Cure is an early term for cross-linking, also frequently used with epoxies.




Figure 8.27 The thermosetting process transformation reaction diagram (112).






to provide an intellectual framework for understanding and comparing the cure and glass transition properties of thermosetting systems. Figure 8.27 illustrates the TTT diagram. Besides Tg, the diagram also displays gelTg, the temperature at which gelation and vitrication occur simultaneously, and Tg0, the glass transition temperature of the reactants. The particular S-shaped curve between Tg0 and Tg results because the reaction rate is increased with increasing temperature. At a temperature intermediate between gelTg and Tg, the reacting mass rst gels, forming a network. Then it vitries, and the reaction stops, incomplete. To the novice, the reaction products may appear complete. This last may result in material failure if the temperature is suddenly raised. The TTT diagram explains why epoxy and similar reactions are carried out in steps, each at a higher temperature. The last step, the postcure, must be done above Tg. Other points shown in Figure 8.27 include the devitrication region, caused by degradation, and the char region, at still higher temperatures.



The discussion above relates to simple homopolymers. Addition of a second component may take the form of copolymerization or polymer blending.