SynopsisA theoretical analysis of the thermoelastic behavior of polymeric networks in swelling equilibrium with excess diluent, using both the kinetic theory of elasticity and the Flory-Huggins theory of mixing, is presented. Our calculations are restricted to the special case of diluents composed of a single constituent. The results are used to obtain the ratio of the energy component of the force fe to the total force f of rubber networks swollen in excess n-decane, and we find fJf to be 0.17, which compares favorably with the value 0.18 reported for the unswollen network. Furthermore, fe/f is independent of elongation, in accordance with theory. The kinetic theory of elasticity is reasonably well obeyed in this highly swollen system although there remains a small contribution to the force from the C? term of the Mooney-Rivlin phenomenological elasticity equation.It is not believed that this has an appreciable effect on fe/f.
SynopsisThe energy component of the stress has been determined for poly(viny1 alcohol) neti works in swelling equilibrium with a series of water-ethylene glycol compositions. The data are analyzed by using the equations describing the thermoelasticity of networks in swelling equilibrium. The ratio fe/f of the energy component to the total force, as calculated from these equations, varies systematically with diluent composition but is independent of elongation in a given diluent. For a network crosslinked by terephthalaldehyde,f,/fvaried from -0.33 to -0.42 as the diluent composition was changed from pure water to 20% ethylene glycol. Similar effects were found in a network crosslinked by formaldehyde. It is not yet certain whether this effect represents a real solvent dependence of fe/f or a failure of the equation of state to account for the effect of composition changes on the force.
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