404

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

8.9

EFFECT OF CRYSTALLINITY ON Tg

405

Figure 8.30 Histogram showing number of times a given value of Tg for linear polyethylene has been reported in the literature by various standard methods indicated (126).

to a confusion with other secondary transitions (see Figure 8.30) (126). Thus various investigators consider the Tg of polyethylene to be in three different regions: -30C, -80C, or -128C. Davis and Eby support the -30C value on the basis of volumetime measurements; Stehling and Mandelkern (127) favor the -128C value based on mechanical measurements. Illers (128) and Boyer (9) support the value of -80C based on extrapolations of completely amorphous ethylenevinyl acetate copolymer data with copolymerTg relationships. Boyer (9) supports the position that -80 is Tg(L) and -30C represents Tg(U ). The transition at -128C is thought to be related to the Schatzki crankshaft motion (Section 8.4.1), although the situation apparently is more complicated (128). Tobolsky (129) obtained -81C for amorphous polyethylene based on a Fox plot [see equation (8.73)] of statistical copolymers of ethylene and propylene, itpolypropylene having a Tg of -18C. 8.9.2 The Nylon Family Glass Transition

Two subfamilies of aliphatic nylons (polyamides) exist: O NH CH2

x NH

O CH2
yC n

(8.76)

from diacids and dibases, and

406

GLASSRUBBER TRANSITION BEHAVIOR

O NH CH2
xC n

(8.77)

originating from w-amino acids. Both subfamilies are semicrystalline; of course, they form commercially important bers. The usually stated Tg range is Tg +40C for polyamide 612 to Tg 60C for polyamide 6 (9); however, Tg depends on the crystallinity of the particular sample. N-methylated polyamides, with a lower hydrogen bonding, have lower Tgs (130). As x and y increase in equations (8.76) and (8.77), the structure becomes more polyethylene-like, and Tg gradually decreases. Interestingly, when x > 4, there is a characteristic mechanical loss peak at about -130C, again suggestive of the Schatzki motion (Section 8.4.1). 8.9.3 Relationships between Tg and Tf

The older literature (131) suggested two relationships between Tg and Tf : Tg/Tf 1 2 2 for symmetrical polymers, and Tg/Tf 3 for nonsymmetrical polymers. Denitions of symmetry differ, however. One method uses the appearance of atoms down the chain: if a central portion of the chain appears the same when viewed from both ends, it is symmetrical. However, even from the beginning, there were many exceptions to the above. The only rule obeyed in this regard is that Tg is always lower than Tf for homopolymers. This is because (a) the same kinds of molecular motion should occur at Tg and Tf, and (b) short-range order exists at Tg, but long-range order exists at Tf. Boyer (9) has prepared a cumulative plot of Tg/Tf (see Figure 8.31). Region 1 A (the old Tg/Tf 2) contains most of the polymers which are free from side groups other than H and F (and hence symmetrical) and contain such polymers as polyethylene, poly(oxymethylene), and poly(vinylidene uoride). Region B contains most of the common vinyl, vinylidene, and condensation polymers such as the nylons. About 55% of all measured polymers lie in the band Tg/Tf = 0.667 0.05 (9). Region C contains poly(a-olens) with long alkyl side groups as well as other nontypical polymers such as poly(2,6dimethylphenylene oxide), which has Tg/Tf approximately equal to 0.93. For 2 an unknown polymer, then, the relationship Tg/Tf = 3 is a good way of providing an estimate of one transition if the temperature of the other is known. 8.9.4 Heat Distortion Temperature

While the glass transition and melting temperatures dene the behavior of polymers from a scientic point of view, the engineers frequently depend on more practical tests. These tests work well for plasticized polymers, blends and composites of various types, and thermosets. These tests originated from the old idea of a softening temperature, sometimes dened as the temperature in

8.9

EFFECT OF CRYSTALLINITY ON Tg

407

Figure 8.31 Range in Tg /Tf values found in the literature. Region A contains unsubstituted polymers. Region C includes poly(a-olens) with long side chains. Region B contains the majority of vinyl, vinylidene, and condensation polymers. The left ordinate is cumulative number, N, and the right ordinate is cumulative percentage of all examples reported as having the indicated Tg /Tf values (9).

which a specimen could be easily penetrated with a needle. One such quantitative test is called the Vicat test, where a needle under 1000 g load penetrates the specimen 1 mm (132). One of the more important of the practical tests is the heat distortion temperature (HDT). The HDT is dened as the temperature at which a 100 mm length, 3 mm thick specimen bar at 1.82 MPa in a three-point bending mode deects 0.25 mm. Youngs modulus at the HDT is 0.75 Gpa (133,134). For unlled polymers, both the Vicat and the HDT tests usually record a temperature just above the glass transition temperature, or for melting conditions, just below the temperature of nal disappearance of crystallinity. For polymer blends, both the Vicat and the HDT will tend to reect the properties of the continuous phase. If the polymer contains ller which raises the modulus, the HDT will be somewhat increased.