8.

EFFECT OF COPOLYMERIZATION ON Tg

399

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

as

illustrating

by

the

timetemperature

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.

8.8

EFFECT OF COPOLYMERIZATION ON Tg

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

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GLASSRUBBER TRANSITION BEHAVIOR

Addition of low-molecular-weight compounds results in plasticization. Experimentally, two general cases may be distinguished: where one phase is retained and where two or more phases result. 8.8.1 One-Phase Systems Based on the thermodynamic theory of the glass transition, Couchman derived relations to predict the Tg composition dependence of binary mixtures of miscible high polymers (113) and other systems (114116). The treatment that follows is easily generalized to the case for statistical copolymers (113). Consider two polymers (or two kinds of mers, or one mer and one plasticizer) having pure-component molar entropies denoted as S1 and S2, and their respective mole fractions (moles of mers for the polymers) as X1 and X2. The mixed system molar entropy may be written S = X1 S1 + X 2 S 2 + DS m (8.64)

where DSm represents the excess entropy of mixing. For later convenience, S1 and S2 are referred to their respective pure-component glass transition tem0 peratures of Tg1 and Tg2, when their values are denoted as S 0 1 and S 2. Heat capacities are of fundamental importance in glass transition theories, because the measure of the heat absorbed provides a direct measure of the increase in molecular motion. The use of classical thermodynamics leads to an easy introduction of the pure-component heat capacities at constant pressure, Cp1 and Cp2:
0 S = X1 S10 + C p1 d ln T + X 2 S 2 + C p 2 d ln T + DS m Tg 1 Tg 2

(8.65)

The mixed-system glass transition temperature, Tg, is dened by the requirement that S for the glassy state be identical to that for the rubbery state, at Tg. This condition and the use of appropriate superscripts G and R lead to the equation
G 0 ,G G G G X1G S10 ,G + C p + Cp 2 d ln T + DS m 1 d ln T + X 2 S 2 Tg 1 Tg 2 R 0 ,R R R R (8.66) = X1R S10 ,R + Tg 1 C p + Cp 1 d ln T + X 2 S 2 2 d ln T + DS m Tg 2

Tg

Tg

Tg

Tg

Since Si0,G = Si0,R (i = 1, 2) and X iG = XiR = Xi, equation (8.66) may be simplied: X1

Tg

Tg 1

G R (C p 1 - C p1 )d ln T + X 2

Tg

Tg 2

G R G R (C p 2 - C p 2 )d ln T + DS m - DS m = 0

(8.67)

8.8

EFFECT OF COPOLYMERIZATION ON Tg

401

In regular small-molecule mixtures, DSm is proportional to X ln X + (1 - X ) ln (1 - X ), where X denotes X1 and X2. Similar relations hold for polymer solvent (plasticizer) and polymerpolymer combinations. Combined with the G R continuity relation, DSm = DSm . For random copolymers these quantities are also equal. Then X1 DC p1 d ln T + X 2
Tg 1 Tg Tg

Tg 2

DC p 2 d ln T = 0

(8.68)

where D denotes transition increments. Again, the increase in the heat capacity at Tg reects the increase in the molecular motion and the increased temperature rate of these motions. After integration the general relationship emerges, Tg Tg =0 + X 2 DC p 2 ln X1 DC p1 ln Tg 2 Tg1 (8.69)

For later convenience the Xi are exchanged for mass (weight) fractions, Mi (recall that the DCpi are then per unit mass), and equation (8.69) becomes ln Tg = or equivalently Tg M 2 DC p 2 ln(Tg 2 Tg1 ) ln = Tg1 M1 DC p1 + M 2 DC p 2 (8.71) M1 DC p1 ln Tg1 + M 2 DC p 2 ln Tg 2 M1 DC p1 + M 2 DC p 2 (8.70)

Equation (8.71) is shown to t Tg data of thermodynamically miscible blends (see Figure 8.28). Four particular nontrivial cases of the general mixing relation may be derived. Making use of the expansions of the form ln(1 + x) = x, for small x, and noting that Tg1/Tg2 usually is not greatly different from unity yield Tg M1 DC p1 Tg1 + M 2 DC p 2 Tg 2 M1 DC p1 + M 2 DC p 2 (8.72)

which has the same form as the Wood equation (117), originally derived for random copolymers. If DCpi Tgi = constant (7678,118), the familiar Fox equation (119) appears after suitable crossmultiplying: M1 M 2 1 = + Tg Tg1 Tg 2 (8.73)

402

GLASSRUBBER TRANSITION BEHAVIOR

Figure 8.28 Glass-transition temperatures, Tg, of poly(2,6-dimethyl-1,4-phenylene oxide) blendpolystyrene (PPO/PS) blends versus mass fraction of PPO, MPPO. The full curve was calculated from equation (8.71) as circles. DCp1 = 0.0671 cal K-1 g-1; DCp2 = 0.0528 cal K-1 g-1; Tg1 = 378 K, Tg2 = 489 K. PPO was designated as component 2 (114,120).

The Fox equation (119) was also originally derived for statistical copolymers (120). This equation predicts the typically convex relationship obtained when T is plotted against M2 (see Figure 8.28). If DCp1 DCp2, the equation of Pochan et al. (121) follows from equation (8.70): ln Tg = M1 ln Tg1 + M 2 ln Tg 2 (8.74)

Finally, if both pure-component heat capacity increments have the same value and the log functions are expanded, Tg = M1Tg1 + M 2Tg 2 (8.75)

which predicts a linear relation for the Tg of the blend, random copolymer, or plasticized system. This equation usually predicts Tg too high. Equations (8.73) and (8.75) are widely used in the literature. Couchmans work (113116) shows the relationship between them. Previously they were used on a semiempirical basis. These equations also apply to plasticizers, a low-molecular-weight compound dissolved in the polymer. In this case the plasticizer behaves as a com-

8.8

EFFECT OF COPOLYMERIZATION ON Tg

403

pound with a low Tg. The effect is to lower the glass transition temperature. A secondary effect is to lower the modulus, softening it through much of the temperature range of interest. An example is the plasticization of poly(vinyl chloride) by dioctyl phthalate to make compositions known as vinyl. 8.8.2 Two-Phase Systems Most polymer blends, as well as their related graft and block copolymers and interpenetrating polymer networks, are phase-separated (122) (see Section 4.3). In this case each phase will exhibit its own Tg. Figure 8.29 (123,124) illustrates two glass transitions appearing in a series of triblock copolymers of different overall compositions. The intensity of the transition, especially in the loss spectra (E), is indicative of the mass fraction of that phase. The storage modulus in the plateau between the two transitions depends both on the overall composition and on which phase is continuous. Electron microscopy shows that the polystyrene phase is continuous in the present case. As the elastomer component increases (small spheres, then cylinders, then alternating lamellae), the material gradually softens. When the rubbery phase becomes the only continuous-phase, the storage modulus will decrease to about 1 108 dynes/cm2.

Figure 8.29 Dynamic mechanical behavior of polystyreneblockpolybutadieneblock polystyrene, a function of the styrenebutadiene mole ratio (123,124).

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GLASSRUBBER TRANSITION BEHAVIOR

Table 8.10 Phase composition of epoxy/acrylic simultaneous interpenetrating networks (125)

Glycidyl Methacrylatea (%) 0 0.3 3.0

a b

Dispersed Phase Weight Fraction PnBAb 0.97 0.82 Epoxy 0.03 0.18

Matrix Phase Weight Fraction PnBA 0.09 0.12 0.30 Epoxy 0.91 0.88 0.70

Grafting mer, increases mixing. Poly(n-butyl acrylate).

If appreciable mixing between the component polymers occurs, the inward shift in the Tg of the two phases can each be expressed by the equations of Section 8.8.1 (125). Using equation (8.73), the extent of mixing within each phase in a simultaneous interpenetrating network of an epoxy resin and poly(n-butyl acrylate) was calculated (see Table 8.10). The overall composition was 80/20 epoxy/acrylic, and glycidyl methacrylate is shown to enhance molecular mixing between the chains. Chapter 13 provides additional material on the glass transition behavior of multicomponent materials.

8.9 EFFECT OF CRYSTALLINITY ON Tg The previous discussion centered on amorphous polymers, with atactic polystyrene being the most frequently studied polymer. Semicrystalline polymers such as polyethylene or polypropylene or of the polyamide and polyester types also exhibit glass transitions, though only in the amorphous portions of these polymers. The Tg is often increased in temperature by the molecular-motion restricting crystallites. Sometimes Tg appears to be masked, especially for highly crystalline polymers. Boyer (9) points out that many semicrystalline polymers appear to possess two glass temperatures: (a) a lower one, Tg(L), that refers to the completely amorphous state and that should be used in all correlations with chemical structure (this transition correlates with the molecular phenomena discussed in previous sections), and (b) an upper value, Tg(U ), that occurs in the semicrystalline material and varies with extent of crystallinity and morphology. 8.9.1 The Glass Transition of Polyethylene Linear polyethylene, frequently referred to as polymethylene, offers a complete contrast with polystyrene in that it has no side groups and has a high degree of crystallinity, usually in excess of 80%. Because of the high degree of crystallinity, molecular motions associated with Tg are partly masked, leading