9.

CONTINUUM THEORIES OF RUBBER ELASTICITY

453

Figure 9.14 A thermally rotated wheel, employing an elastomer as the working substance (51).

where QI and QII are the amounts of heat released to the low-temperature reservoir (T I) and absorbed from the high-temperature reservoir (T II), respectively. While the entropy change is zero for either system during the reversible adiabatic steps (see Figures 9.12c and 9.13c), it must be emphasized that the entropy change is greater than zero for an irreversible adiabatic process. An example for an elastomer is letting go of a stretched rubber band. 9.8.4 An Elastomer Thermal Cycle Demonstration

The elastomer thermal cycle is demonstrated in Figure 9.14 (51). A bicycle wheel is mounted on a stand, with a source of heat on one side only. Stretched rubber bands replace the spokes. On heating, the stress that the stretched rubber bands exert is increased so that the center of gravity of the wheel is displaced toward 9 oclock in the drawing. The wheel then rotates counterclockwise (52). Each of the steps in Figure 9.13 may be traced in Figure 9.14, although none of the steps in Figure 9.13 are purely isothermal or adiabatic, and then of course they are not strictly reversible. Steps 1 to 2 in Figure 9.13 occur at 6 oclock in Figure 9.14, where there is a (near) adiabatic length increase due to gravity. At 3 oclock, at T II, heat is absorbed (nearly) isothermally, and the length decreases, doing work.At 12 oclock, corresponding to steps 3 to 4, there is an adiabatic length decrease due to gravity. Last, at 9 oclock, steps 4 to 1, there is a (nearly) isothermal length increase, and heat is given off to the surroundings at T I, and work is done on the elastomer.

9.9 CONTINUUM THEORIES OF RUBBER ELASTICITY 9.9.1 The MooneyRivlin Equation

The statistical theory of rubber elasticity is based on the concepts of random chain motion and the restraining power of cross-links; that is, it is a molecular

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CROSS-LINKED POLYMERS AND RUBBER ELASTICITY

theory. Amazingly, similar equations can be derived strictly from phenomenological approaches, considering the elastomer as a continuum. The best known such equation is the MooneyRivlin equation (5356), 1 1 s = 2C1 a - 2 + 2C 2 1 - 3 a a which is sometimes written in the algebraically identical form, 2C 2 1 s = 2C1 + a- 2 a a (9.49) (9.48)

Equations (9.48) and (9.49) appear to have a correction term for equation (9.34), with an additional term being added. However, they are derived from quite different principles. According to equation (9.34), the quantity s/(a - 1/a 2) should be a constant. Equation (9.49), on the other hand, predicts that this quantity depends on a: 2C 2 s = 2C1 + 2 a a -1 a (9.50)

Plots of s/(a - 1/a 2) versus 1/a are found to be linear, especially at low elongation (see Figure 9.15) (57). The intercept on the a-1 = 0 axis yields 2C1, and the slope yields 2C2. The value of 2C1 varies from 2 to 6 kg/cm2, but the value of 2C2, interestingly, remains constant near 2 kg/cm2. Appendix 9.2 describes a demonstration experiment that illustrates both rubber elasticity [see equation (9.34)] and the nonideality expressed by equation (9.50). On swelling, the value of 2C2 drops rapidly (see Figure 9.16) (57), reaching a value of zero near v2 (volume fraction of polymer) equal to 0.2. This same dependence is observed for the same polymer in different solvents, different levels of cross-linking for the same polymer, or (as shown) different polymers entirely (57). The interpretation of the constants 2C1 and 2C2 has absorbed much time; the results are inconclusive (42). It is tempting but generally considered 2 ). The original derivation of Mooney incorrect to equate 2C1 and nRT(ri2/r0 (46) shows that 2C2 has to be nite, but it does not indicate its value relative to 2C1. According to Flory (41), the ratio 2C2/2C1 is related to the looseness with which the cross-links are embedded within the structure. Trifunctional cross-links have larger values of 2C2/2C1 than tetrafunctional cross-links, for example (58). As indicated above, 2C2 decreases with the degree of swelling. Furthermore Gee (59) showed that during stress relaxation, swelling increased the rate of approach to equilibrium. Ciferri and Flory (60) showed that 2C2 is markedly

9.9

CONTINUUM THEORIES OF RUBBER ELASTICITY

455

Figure 9.15 Plot of s/(a - 1/a 2) versus a-1 for a range of natural rubber vulcanizates. Sulfur content increases from 3 to 4%, with time of vulcanization and other quantities as variables (57).

reduced by swelling and deswelling the sample at each elongation. The samples, actually measured dry, had 2C2 values about half as large after the swellingdeswelling operation as those measured before. These results suggest that the magnitude of 2C2 is caused by nonequilibrium phenomena. Gumbrell et al. (57) stated it in terms of the reduced numbers of conformations available in the dry state versus the swollen state. Other possible explanations include non-Gaussian chain or network statistics (see Section 9.10.6) and internal energy effects (42). The latter, bearing on the front factor, will be treated in Section 9.10. 9.9.2 Generalized StrainEnergy Functions

Following the work of Mooney, more generalized theories of the stressstrain relationships in elastomers were sought. The central problem was how to calculate the work, W, stored in the body as strain energy. Rivlin (56) considered the most general form that such strainenergy functions could assume. As basic assumptions, he took the elastomer to be incom-

456

CROSS-LINKED POLYMERS AND RUBBER ELASTICITY

Figure 9.16 Dependence of C2 on v2 for synthetic rubber vulcanizates (57). Polymers: , butadienestyrene, (95/5); , butadienestyrene, (90/10); , butadienestyrene, (85/15); , butadienestyrene, (75/25); , butadienestyrene, (70/30); X, butadieneacrylonitrile, (75/25).

pressible and isotropic in the unstrained state. Symmetry conditions required that the three principal extension ratios, a1, a2, and a3, depend only on even powers of the as. In three dimensions (see Figure 9.17), the simplest functions that satisfy these requirements are
2 2 2 I1 = a 1 +a2 +a3

(9.51)
2 3 2 1

I2 = a a + a a + a a
2 1 2 2 2 2 2 3

(9.52) (9.53)

I3 = a a a
2 1 2 2

2 3

where I1, I2, and I3 are termed strain invariants. The third strain invariant is equal to the square of the volume change, V =1 I3 = V0
2

(9.54)

9.9

CONTINUUM THEORIES OF RUBBER ELASTICITY

457

Figure 9.17 An elastomeric cube. (a) Undeformed and (b) deformed states, showing principal stresses and strains.

which under the assumption of incompressibility equals unity. Alternate formulations have been proposed by Valanis and Landel (61) and by Ogden (62), which have been reviewed by Treloar (42). Consider the deformation of a cube (Figure 9.17). The work that is stored in the body as strain energy can be written (63). W (a ) = s 1 da1 + s 2 da 2 + s 3 da 3 (9.55)

where the s s are the stresses. The work, in a more general form, can be expressed as a power series (56): W=

i , j ,k = 0

Cijk (I 1 - 3) (I 2 - 3) (I 3 - 1)

(9.56)

Equation (9.56) is written so that the strain energy term in question vanishes at zero strain. For the lowest member of the series, i = 1, j = 0, and k = 0, W = C100 (I 1 - 3) (9.57)

which is functionally identical to the free energy of deformation expressed in equation (9.31). For the case of uniaxial extension, a1 = a and noting equation (9.32) and equation (9.54), 1 a2 = a3 = a
1 2

(9.58)

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CROSS-LINKED POLYMERS AND RUBBER ELASTICITY

Equation (9.57) can now be written 2 W = C100 a 2 + a and the stress can be written [see equation (9.54)] s= W 1 = 2C100 a - 2 a a (9.60) (9.59)

This equation is readily identied with equation (9.34), suggesting (for this case only) that 2C100 = nRT ri 2 r02 (9.61)

On retention of an additional term in equation (9.55), with i = 0, j = 1, and k = 0, W = C100 (I 1 - 3) + C010 (I 2 - 3) (9.62)

which leads directly to the MooneyRivlin equation, equation (9.49). Interestingly, if we retain one more term, C200, an equation of the form (63) C 1 s = C+ + C a 2 a - 2 a a can be written, where C = 2(C100 - 6C 200 ) C = 2(4C 200 + C010 ) and C = 4C 200 (9.66) (9.64) (9.65) (9.63)

Equation (9.63), with two additional terms over the statistical theory of rubber elasticity, ts the data quite well (see Figure 9.18) (64). Because no particular molecular model was assumed, theoretical values cannot be assigned to C, C, and C, nor can any molecular mechanisms be assigned. These phenomenological equations of state, however, accurately express the form of the experimental stressstrain data.

9.10

SOME REFINEMENTS TO RUBBER ELASTICITY

459

Figure 9.18 MooneyRivlin plot for sulfur-vulcanized natural rubber. Solid line, equation (9.48); dotted line, equation (9.63).

9.10

SOME REFINEMENTS TO RUBBER ELASTICITY

The statistical theory of rubber elasticity has undergone signicant and continuous renement, resulting in a series of correction terms. These are sometimes omitted and sometimes included in scientic and engineering research, as the need for them arises. In this section we briey consider some of these. 9.10.1 The Inverse Langevin Function The Gaussian statistics leading to equation (9.34) are valid only for relatively small strainsthat is, under conditions where the contour length of the chain is much more than its end-to-end distance. In the region of high strains, where 1 1 the ratio of the two parameters approaches 3 to 2 , this limit is exceeded. Kuhn and Grn (65) derived a distribution function based on the inverse Langevin function. The Langevin function itself can be written L( x) = coth x 1 x (9.67)

and was rst applied to magnetic problems. In this case L(b ) = r n l (9.68)

where n is the number of links of length l. (It must be pointed out that the quantity n in this case need not be identical with the number of mers in the chains.) Thus the quantity nl represents a measure of the contour length of the chain, and r/nl is the fractional chain extension. Of course, for the inverse Langevin function of interest here,