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Table 9.1

Corresponding concepts in ideal gases and ideal elastomers

PV = nRT Entropy calculated from probabilities of nding n molecules in a given volume Probability of the gas volume spontaneously decreasing (U/V )T = 0; internal energy assumed zero Molar volume of gas assumed zero Pressure P given by -(F/V )T

G = nRT Entropy calculated from probability of nding end-to-end distance r at r0 Probability of an elastomer strip spontaneously elongating (U/V )T,V = 0; internal energy assumed constant Elastomer assumed incompressible (molar volume is constant) Retractive force f given by -(F/V )T,V

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STATISTICAL THERMODYNAMICS OF RUBBER ELASTICITY

It is useful to consider again the freely jointed chain (Section 5.3.1). In this 2 1/2 case the root-mean-square end-to-end distance is given by ( r = ln1/2. In a f ) 2 1/2 real random coil, with xed bond angles, the quantity (rf ) is larger but still obeys the n1/2 relationship. For a given value of n, however, the root-meansquare end-to-end distance can vary widely, from zero, where the ends touch, to nl, the length of the equivalent rod. The probability of nding particular values of r underlies the following subsections. 9.7.1 The Equation of State for a Single Chain

It is convenient to divide the derivation of equations such as (9.4) into two parts. First, the equation of state for a single chain in space is derived. Then we show how a network of such chains behaves. It is convenient to start again with the general equation for the Helmholtz free energy, equation (9.5): F = U - TS This can be rewritten in statistical thermodynamic notation: F = constant - kT ln W(r , T ) (9.19)

where the quantity W(r, T ) [see equations (9.12) and (9.13)] now refers to the probability that a polymer molecule with end-to-end distance r at temperature T will adopt a given conformation. From a quantitative point of view, at each particular end-to-end distance, all possible conformations of the chain need to be counted, holding the ends
The term conformation refers to those arrangements of a molecule that can be attained by rotating about single bonds. Congurations refer to tacticity, steric arrangement, cis and trans, and so on; see Chapter 2.

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xed in space. Then the sum of all such conformations as the end-to-end distance is varied needs to be calculated. (Later the sum of all conformations of a distribution of molecular weights is considered.) The retractive force is given by f= F ln W(r , T ) = -kT r T ,V T ,V r (9.20)

As before, the quantity U, assumed to be constant (or zero), drops out of the calculation, leaving only the entropic contribution. In this case, for a single chain, the quantity f for force must be used. The cross section of the individual chain, necessary for a determination of the stress, remains undened. A particular direction in space is selected rst. Then, using vector notation, the probability that r lies between r and r + dr in that direction is given by W (r ) dr = W(r , T ) dr (9.21)

W(r , T ) dr

where the denominator serves as a normalizing factor. Of course, the integral does not need to extend to innity; in reality different conformations only go to the fully extended, rodlike chain. Removing the directional restrictions on r, W (r ) dr = W(r , T ) dr 4pr 2 (9.22)

W(r , T ) dr

A spherical shell between r and r + dr is generated (see Figure 9.9), depicted in Cartesian coordinates. Rearranging equation (9.22) and taking logarithms, ln W(r , T ) = ln W (r ) + ln W(r , T ) dr - ln 4p - ln r 2
0

(9.23)

Differentiating with respect to r, 2 ln W(r , T ) ln W (r ) = r r r T ,V T ,V since W(r , T ) dr is independent of r. 0 The quantity W(r) can be expressed as a Gaussian distribution (18): W (r ) = b - b2r2 4pr 2 e p1 2
3

(9.24)

(9.25)

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Figure 9.9 A spherical shell at a distance r (inner surface) and r + dr (outer surface), dening all conformations in space having that range of r.

Figure 9.10 The radial distribution function W(r ) as a function of r for (a) a relaxed chain, where the most probable end-to-end distance is r0, and (b) for a chain under an extensive force, f.

2 2 In molecular terms, b 2 = 3/(2r0 ), where r0 represents the average of the squares of the relaxed end-to-end distances. The quantity W(r) is shown as a function of r in Figure 9.10. The radial distribution function W(r) is shown for a relaxed chain and a chain extended by a force f. Equation (9.24) can now be expressed as ln W(r , T ) = -2b 2 r T ,V r Substituting equation (9.26) into equation (9.20), (9.26)

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f=

3kTr r02

(9.27)

and the equation of state for a single chain is obtained. The force appears to be zero at r = 0, because of the spherical shell geometry assumed (Figure 9.9). Again, the quantity r0 is the isotropic end-to-end distance for a free chain in space. This approximates the end-to-end distance expected both in q-solvents and in the bulk state, for linear chains. 9.7.2 The Equation of State for a Macroscopic Network

Equation (9.27) expresses the retractive force of a single chain on extension. Since the retractive force is proportional to the quantity r, the chain behaves as a Hookean spring on extension. The problem now is to link a large number, n, of these chains together per unit volume to form a macroscopic network. The assumption of afne deformation is required; that is, the junction points between chains move on deformation as if they were embedded in an elastic continuum (Figure 9.11). The mean square length of a chain in the strained state is given by
2 2 2 (a x )ri2 r2 = 1 +ay +az 3

(9.28)

The alphas represent the fractional change in shape in the three directions, equal to (L/L0)i, where i = x, y, or z. The quantity ri2 represents the isotropic, unstrained end-to-end distance in 2 the network. The two quantities ri2 and r0 [see equation (9.27)] bear exact comparison.They represent the same chain in the network and un-cross-linked 2 states, respectively. Under many circumstances the quantity ri2/r0 approximately equals unity. In fact the simpler derivations of the equation of state for rubber elasticity do not treat this quantity, implicitly assuming it to be unity (42). However, deviations from unity may be caused by swelling, cross-linking while in tension, changes in temperature, and so on, and play an important role in the development of modern theory. The difference between ri and r0 may be illustrated by way of an example. Assume a cube of dimensions 1 1 1 cm. Its volume, of course, is 1 cm3. If it is swelled to 10 cm3 volume, then each linear dimension in the sample is increased by (10)1/3, the new length of the sides, in this instance. Assuming an afne deformation, the end-to-end distance of the chains will also increase by (10)1/3; that is, ri = (10)1/3r0. The value of r0 does not change, because it is the end-to-end distance of the equivalent free chain. The value of ri is determined by the distances between the cross-link sites binding the chain. Again, neither ri nor r0 represents the end-to-end distance of the whole primary chain but rather the end-to-end distance between cross-link junctions.

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Figure 9.11 Illustration of an afne deformation, end-to-end vectors drawn from a central point. (a) End-to-end vectors have spherical symmetry. (b) After extending the macroscopic sample, end-to-end vectors have ellipsoidal symmetry. Parts (c) and (d ) illustrate the corresponding effects on a single chain.

For the work done by the n network chains, -W = DFel (9.29)

where DFel represents the change in the Helmholtz free energy due to elastic deformation. Returning to equation (9.27), for n chains, DFel = 3nRT r02

(r2) ( ri2 )1 2 r dr
12

(9.30)

Integrating and substituting equation (9.28) yields DFel = nRT ri 2 2 (a x + a y2 + a z2 - a x20 - a y20 - a z20 ) 2 r02 (9.31)

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2 2 By denition, a 2 x0 = a y0 = a z0 = 1, since these terms deal with the unstrained state. Since it is assumed that there is no volume change on deformation (Poissons ratio very nearly equals 0.5, i.e., an incompressible solid),

a xa ya z = 1

(9.32)

If ax is taken simply as a, then az = ay = 1/a1/2, at constant volume. After making the above substitutions, the work on elongation equation may be written, per unit volume, -W = DFel = The stress is given by s= ri 2 1 F = nRT a- 2 a T ,V 2 a r0 (9.34) nRT ri 2 2 2 a + -3 2 r02 a (9.33)

which is the equation of state for rubber elasticity. Equation (9.34) bears 2 is known as the front comparison with equation (9.4). The quantity ri2/r0 factor. The quantity n in the above represents the number of active network chains per unit volume, sometimes called the network or cross-link density. The number of cross-links per unit volume is also of interest. For a tetrafunctional cross-link (see Figure 9.3), the number of cross-links is one-half the number of chain segments (see Section 9.9.2). Equation (9.34) holds for both extension and compression. Several other relationships may be derived immediately. Youngs modulus can be written s E=L L T ,V which yields E = nRT ri 2 ri 2 2 1 @ 3n RT 2a + a r02 r02 (9.36) (9.35)

for small strains. This is the engineering modulus, which utilizes the actual cross section at a rather than the relaxed value (i.e., a = 1). At low extensions, the two moduli are nearly identical. The shear modulus may be written

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G = E 2(1 + v)

(9.37)

Poissons ratio, v, for rubber is approximately 0.5 (incompressibility assumption), so G=n Then, to a good approximation 1 s =G a - 2 a (9.39) ri 2 r02 RT (9.38)

thus dening the work to stretch, the stressstrain relationships, and the modulus of an ideal elastomer. As equations (9.34) and (9.39) illustrate, the stressstrain relationships are non-Hookean; that is, the strain is not proportional to the stress. Again, these equations yield curves of the type illustrated in Figures 9.5 and 9.7. These same equations can also be used for compression. For compression, of course, a < 1 (49). Another relationship treats biaxial extension (50). If equibiaxial extension is assumed, such as in a spherical rubber balloon, then s = nRT (a 2 - a -4 ) (9.40)

2 assuming r i2/r 0 @ 1, and the volume changes of the elastomer on biaxial extension are nil. Other moduli are occasionally used to characterize polymeric materials. Appendix 9.1 describes the use of the ball indentation method to characterize the cross-link density of gelatin. In general, this method can be used for sheet rubber and other large sample types.

9.7.3

Some Example Calculations

9.7.3.1 An Example of Rubber Elasticity Calculations Suppose that an elastomer of 0.1 cm 0.1 cm 10 cm is stretched to 25 cm length at 35C, a stress of 2 107 dynes/cm2 being required. What is the concentration of active network chain segments? 2 Use equation (9.34), assuming that ri2 = r0 . n= = s RT (a - 1 a 2 ) 2 10 7 dynes cm 2 8.31 10 (dynes cm mol K) 308 K (2.5 - 1 2.5 2 )
7

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noting that a = L/L0 = 25/10 = 2.5. n = 3.34 10 -4 mol cm 3 Note that the rubber band in Appendix 9.2 has n = 1.9 10-4 mol/cm3. 9.7.3.2 An Example of Work Done during Stretching The elastomer strip in Section 9.7.3.1 was stretched to 45 cm length at 25C. How much work was required? Equation (9.33) provides the basis. The quantity r i2/r 2 0 is taken as substan-4 3 tially unity. The quantity n = 3.34 10 mol/cm . -W = 3.34 10 -4 (mol cm 3 ) 8.31 10 7 (dyn cm mol K) 298 K(4.5 2 + 2 4.5 - 3) -W = 1.46 10 8 erg cm 3 , noting that dyn cm erg But noting that there are 10 cm3 of elastomer, -W = 1.46 10 9 erg or 1.46 10 2 J This calculation ignores the mass of the elastomer itself. Note that work, as given in equation (9.33), must have units that match the units of the gas constant R. 9.7.3.3 An Example Using Mc In Section 9.4, the quantity n, the number of active network chain segments per unit volume, was shown to be equal to the density over the molecular weight between cross-links, r/Mc. Suppose an amorphous polymer of Tg = -10C, and of density r = 1.10 g/cm3 was chemically cross-linked, such that a cross-link was placed every 10,000 g/mol of chain. What is Youngs modulus at 25C? (Note that since Tg is well below 25C and the polymer is cross-linked, the polymer is in the rubbery plateau region.) In this case, Mc = 1 104 g/mol. n = r M c = 1.10 g cm 3 l 10 4 g mol n = 1.1 10 -4 mol cm 3 = 1.1 10 2 mol m 3 Youngs modulus is given by equation (9.36): E = 3nRT = (3 1.1 10 2 mol m 3 ) (8.314 Pa-m 3 mol - K) 298 K E = 8.16 10 5 Pa = 8.16 10 6 dyn cm 2 This result suggests a soft elastomer, but the effects of physical entanglements were ignored, see Section 9.10.5, so the nal Youngs modulus will be somewhat higher.