450

CROSS-LINKED POLYMERS AND RUBBER ELASTICITY

9.8

THE CARNOT CYCLE FOR ELASTOMERS

In elementary thermodynamics, the Carnot cycle illustrates the production of useful work by a gas in a heat engine. This section outlines the corresponding thermodynamic concepts for an elastomer and illustrates a demonstration experiment. The conservation of energy for a system may be written dU = V dp + T dS + s dL + . . . (9.41)

where the internal energy, U, is equated to as many variables as exist in the system. For an ideal gas (Section 9.6), P-V-T variables are selected. The corresponding variables for an ideal elastomer are s-L-T [see equation (9.34)]. Since Poissons ratio is nearly 0.5 for elastomers, the volume is substantially constant on elongation. By carrying a gas, elastomer, or any material through the appropriate closed loop with a high- and low-temperature portion, they may be made to perform work proportional to the area enclosed by the loop. A system undergoing such a cycle is called a heat engine. 9.8.1 The Carnot Cycle for a Gas

In the Carnot heat engine, a gas is subjected to two isothermal steps, which alternate with two adiabatic steps, all of which are reversible (see Figure 9.12) (48). Briey, the gas undergoes a reversible adiabatic compression from state 1 to state 2. The temperature is increased from T1 to T2. During this step the surroundings do work |w 12| on the gas. The absolute signs are used because conventions require that the signs on some of the algebraic quantities herein be negative. Next the gas undergoes a reversible isothermal expansion from state 2 to state 3. While expanding, the gas does work |w 23| on the surroundings while absorbing heat |q2|. Then there follows a reversible adiabatic expansion of the gas from state 3 to state 4, the temperature dropping from T2 to T1. During this step, the gas does work |w 34| on the surroundings. Last, there is an isothermal compression of the gas from state 4 to state 1 at T1. Work |w41| is performed on the gas, and heat |q1| ows from the gas to the surroundings. 9.8.2 The Carnot Cycle for an Elastomer

For an elastomer, the rubber goes through a series of stresslength steps, two adiabatically and two isothermally, as in the Carnot cycle (see Figure 9.13) (51). Beginning at length L1 and temperature T I, a stress, s, is applied stretching the elastomer adiabatically to L2. The elastomer heats up to T II. The quantity s is related to the length by the nonlinear equation

9.8

THE CARNOT CYCLE FOR ELASTOMERS

451

Figure 9.12 Carnot cycle for a gas (48).

L L0 s = nRT L0 L

(9.42)

[see equation (9.34)]. In this step work is done on the elastomer. At T II, the elastomer is allowed to contract isothermally to L3. It absorbs heat from its surroundings in this step and does work. As the length decreases, its entropy increases by DS (see Figure 9.13c). The elastomer then is allowed to contract adiabatically to L4, doing work, and its temperature falls to T I again. The length of the sample is then increased isothermally from L4 to L1, work being done on the sample, and heat is given off to its surroundings. This step completes the cycle. An increase in the volume of the gas, however, corresponds to a decrease in the length of a stretched elastomer. It is important to note that at no time does the elastomer come to its rest length, L0. Interestingly the corresponding rest volume of a gas is innitely large. 9.8.3 Work and Efciency

The equations governing the work done during the two cycles may also be compared. For a gas, w g = - P dV (9.43)

452

CROSS-LINKED POLYMERS AND RUBBER ELASTICITY

Figure 9.13 Thermal cycle for an elastomer (51).

For an elastomer, w e = - s dL (9.44)

In both cases the cyclic integral measures the area enclosed by the four steps in Figures 9.12 and 9.13. , of the two systems may also be compared. For a gas, The efciencies, h hg = q1 + q2 q2 (9.45)

where q1 and q2 are the heat absorbed and released (opposite signs), as above. For the elastomer, he = or in a different form, he = T II - T I T II (9.47)

s dL = (T
QII

II

- T I ) DS QI + QII = QII QII

(9.46)

9.9

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 9.9.1

CONTINUUM THEORIES OF RUBBER ELASTICITY 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