9.

11 INTERNAL ENERGY EFFECTS

469

Figure 9.26 Model of the end-pulling mechanism, showing how R|| increases, while R^ remains nearly constant: (A) relaxed and (B ) stretched.

styrene had a molecular weight of 5 105 g/mol. The anisotropy of the Rg values agreed with those predicted on the basis of a chain afne model. While general conclusions appear to be premature, it appears that the crosslink sites rearrange themselves during deformation to achieve their lowest free-energy states; thus the chains deform less than the afne mechanisms predicts. A modied end-pulling mechanism is also possible. A possible molecular mechanism, which results in minimal changes in R^, is illustrated in Figure 9.26 (107). The debate over the exact molecular mechanism of deformation is sure to continue.

9.11 INTERNAL ENERGY EFFECTS 9.11.1 Thermoelastic Behavior of Rubber

In Section 9.5 some of the basic classical thermodynamic relationships for rubber elasticity were examined. Now the classical and statistical formulations are combined (108,109). Rearranging equation (9.8), fe = f - T f T L ,V (9.85)

Dividing through by f and rearranging, fe ln f = 1 ln T L ,V f (9.86)

Rewriting equation (9.79) in terms of force, and substituting equation (9.38), we nd that

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CROSS-LINKED POLYMERS AND RUBBER ELASTICITY

V 1 f = GA0 a V0 a 2

(9.87)

where A0 is the initial cross-sectional area; substituting equation (9.87) into the right-hand side of equation (9.86) and carrying out the partial derivative yields d ln G bT ln f = + ln T L ,V d ln T 3 (9.88)

where b is the isobaric coefcient of bulk thermal expansion, (1/V )(V/T )L,P. Substituting equation (9.88) into equation (9.86), fe d ln G bT = 1f 3 d ln T (9.89)

Returning to equation (9.38), and differentiating the natural logarithm of the network end-to-end distance with respect to the natural logarithm of the temperature obtains d ln r02 d ln G bT = 1d ln T d ln T 3 (9.90)

Nothing that the right-hand sides of equations (9.89) and (9.90) are identical, fe d ln r02 1 d ln r02 = = f d ln T T dT (9.91)

which expresses the fractional force due to internal energy considerations in terms of the temperature coefcient of the free chains end-to-end distance. 9.11.2 Experimental Values

Values of fe/f are usually derived by applying the equations above to forcetemperature data of the type presented in Figure 9.27 (110). These data, carefully taken after extensive relaxation at elevated temperatures, are reversible within experimental error; that is, the same result is obtained whether the temperature is being lowered (usually rst) or raised. Some values of fe/f are shown in Table 9.2. For most simple elastomers, fe/f is a small fraction, near 0.20 or less. This indicates that some 80% or more of the retractive force is entropic in nature, as illustrated from early data in

9.11 INTERNAL ENERGY EFFECTS

471

Figure 9.27 Forcetemperature relationships for natural rubber. Extension ratios, a, are indicated by the numbers associated with the lines (110).

Table 9.2

Thermoelastic behavior of various polymers

Polymer Natural rubber trans-Polyisoprene cis-Polybutadiene Polyethylene Poly(ethyl acrylate) Poly(dimethyl siloxane)

fe/f 0.12 0.17 0.10 -0.42 -0.16 0.15

Reference (a) (b) (c) (d) (e) (e)

References: (a) G. Allen, M. J. Kirkham, J. Padget, and C. Price, Trans. Faraday Soc., 67, 1278 (1971). (b) J. A. Barrie and J. Standen, Polymer, 8, 97 (1967). (c) M. Shen, T. Y. Chem. E. H. Cirlin, and H. M. Gebhard, in Polymer Networks, Structure, and Mechanical Properties, A. J. Chompff and S. Newman, eds., Plenum Press, New York, 1978. (d) A. Ciferri, C. A. J. Hoeve, and P. J. Flory, J. Am. Chem. Soc., 83, 1015 (1961). (e) L. H. Sperling and A. V. Tobolsky, J. Macromol. Chem., 1, 799 (1966).

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CROSS-LINKED POLYMERS AND RUBBER ELASTICITY

Figure 9.7. These same values, of course, lead to temperature coefcients of polymer chain expansion [equation (9.91)].

9.12 9.12.1

THE FLORYREHNER EQUATION Causes of Swelling

The equilibrium swelling theory of Flory and Rehner (76) treats simple polymer networks in the presence of small molecules. The theory considers forces arising from three sources: 1. The entropy change caused by mixing polymer and solvent. The entropy change from this source is positive and favors swelling. 2. The entropy change caused by reduction in numbers of possible chain conformations on swelling. The entropy change from this source is negative and opposes swelling. 3. The heat of mixing of polymer and solvent, which may be positive, negative, or zero. Usually it is slightly positive, opposing mixing. The FloryRehner equation may be written v2 13 2 - [ln(1 - v2 ) + v2 + c1v2 ] = V1 n v2 - 2 (9.92)

where v2 is the volume fraction of polymer in the swollen mass, V1 is the molar volume of the solvent, and c1 is the FloryHuggins polymersolvent dimensionless interaction term. Appendix 9.3 describes the application of the FloryRehner theory. This theory, of course, is also related to the thermodynamics of solutions (see Section 3.2). As a rubber elasticity phenomenon, it is an extension in three dimensions. The value of equation (9.92) here lies in its complementary determination of the quantity n [see equation (9.4) for simplicity]. Both equations (9.4) and (9.92) determine the number of elastically active chains per unit volume (containing, implicitly, corrections for front factor changes). By measuring the equilibrium swelling behavior of an elastomer (c1 values are known for many polymersolvent pairs), its modulus may be predicted. Vice versa, by measuring its modulus, the swelling behavior in any solvent may be predicted. Generally, values from modulus determinations are somewhat higher, because physical cross-links tend to count more in the generally less relaxed mechanical measurements than in the closer-to-equilibrium swelling data. However, agreement is usually within a factor of 2, providing signicant interplay between swelling and modulus calculations (111113).

9.13

GELATION PHENOMENA IN POLYMERS

473

Simple elastomers may swell a factor of 4 or 5 or so, leading to a quantitative determination of n. However, two factors need to be considered before the nal numerical results are accepted: 1. The front-factor, not explicitly stated in the FloryRehner equation, may be signicantly different from unity (114). 2. While step polymerization methods lead to more or less statistical networks and good agreement with theory, addition polymerization and vulcanization nonuniformities lead to networks that may swell as much as 20% less than theoretically predicted (115,116). 9.12.2 Example Calculation of Youngs Modulus from Swelling Data

At equilibrium, a sample of poly(butadienestatstyrene) swelled 4.8 times its volume in toluene at 25C. What is Youngs modulus at 25C? This material is a typical elastomer, widely used for rubber bands, gaskets, and rubber tires. Table 3.4 gives c1 = 0.39. The molar volume of toluene can be calculated from its density, 0.8669 g/cm3, Table 3.1. A molecular weight of 92 g/mol for toluene yields a molar volume of 106 cm3/mol. The quantity v2 = 1/4.8 = 0.208. Substituting into equation (9.92) yields n= - [ln(1 - 0.208) + 0.208 + 0.39 0.208 2 ] (106 cm 3 mol){0.2081 3 - 0.208 2}

n = 1.5 10 -4 mol cm 3 Youngs modulus is given by equation (9.36), E = 3 1.5 10 -4 (mol cm 3 ) 8.31 10 7 (dyn cm mol K) 298(K) E = 1.1 10 7 dyn cm 2 or 1.1 MPa

This is a typical Youngs modulus for such elastomers. Of course, the reverse calculation can be performed, starting with the modulus, and estimating the equilibrium swelling volume.

9.13

GELATION PHENOMENA IN POLYMERS

Gelation in polymers may be brought about in several ways: temperature changes, particularly important in protein gelation formation; polymerization with cross-links; phase separation in block copolymers; ionomer formation; or even crystallization. Such materials are usually thermoreversible for physical cross-links, or thermoset through the advent of chemical cross-links. Of course, there must be at least two cross-link sites per chain to induce gelation. A major