Entropy elasticity thermodynamics

Values for tte internal variabtes in thetmodynamic, internal equilibriwn are generally uniquely defined by the values for the external variables. For instance, in a simple, thermomechanical system (i.e. one that reacts mechanically solely volume-elastically) the equilibrium concentrations of the conformational isomers are uniquely described by temperature and pressure. In this case the conformational isomerism is not explicitly percqitible, but causes only overall effects, for example in the system s enthalpy or entropy. Elastic macroscopic effects may, however, occur when the relationship between internal and external variables is not single-valued. Then the response-functions of the system diverge or show discontinuities. The Systran undergoes a thermodynamic transformation. The best-known example of sudi a transformation based on conformational isomerism is the helix-coil transition displayed by sonte polymers in solution. An example in the scdid state is the crystal-to-condis crystal transition discussed in this paper. The conditions under which such transformations occur are dealt with in more detail in Sect 2.2. 

The changes in the states of entropy-elastic bodies described in the previous section can be expressed quantitatively by phenomenological thermodynamics, starting with one of the fundamental equations in thermodynamics. The relationship of interest here relates the pressure p with the internal energy (7, the volume F, and the thermodynamic temperature T (see textbooks of chemical thermodynamics) ... 

The behavior of weakly cross-linked rubber was described in Section 11.1 as entropy-elastic. If this material is deformed, the chains are displaced from their equilibrium positions and brought into a state which is en-tropically less favorable. Because of the weak cross-linking, the chains are unable to slip past one another. On relaxation, the chains return from the ordered position to a disordered one the entropy increases. The phenomenon can be described in various ways. Seen thermodynamically, the rubber elasticity is related to a lowering of entropy on deformation. From the molecular point of view, the molecular particles are forced to adopt an... 

These fascinating bicontinuous or sponge phases have attracted considerable theoretical interest. Percolation theory [112] is an important component of such models as it can be used to describe conductivity and other physical properties of microemulsions. Topological analysis [113] and geometric models [114] are useful, as are thermodynamic analyses [115-118] balancing curvature elasticity and entropy. Similar elastic modulus considerations enter into models of the properties and stability of droplet phases [119-121] and phase behavior of microemulsions in general [97, 122]. 

It is not particularly difficult to introduce thermodynamic concepts into a discussion of elasticity. We shall not explore all of the implications of this development, but shall proceed only to the point of establishing the connection between elasticity and entropy. Then we shall go from phenomenological thermodynamics to statistical thermodynamics in pursuit of a molecular model to describe the elastic response of cross-linked networks. 

Since entropy plays the determining role in the elasticity of an ideal elastomer, let us review a couple of ideas about this important thermodynamic variable ... 

There are three different approaches to a thermodynamic theory of continuum that can be distinguished. These approaches differ from each other by the fundamental postulates on which the theory is based. All of them are characterized by the same fundamental requirement that the results should be obtained without having recourse to statistical or kinetic theories. None of these approaches is concerned with the atomic structure of the material. Therefore, they represent a pure phenomenological approach. The principal postulates of the first approach, usually called the classical thermodynamics of irreversible processes, are documented. The principle of local state is assumed to be valid. The equation of entropy balance is assumed to involve a term expressing the entropy production which can be represented as a sum of products of fluxes and forces. This term is zero for a state of equilibrium and positive for an irreversible process. The fluxes are function of forces, not necessarily linear. However, the reciprocity relations concern only coefficients of the linear terms of the series expansions. Using methods of this approach, a thermodynamic description of elastic, rheologic and plastic materials was obtained. 

For the purpose of illustrating the application of the thermodynamic equation of state to experimental data, consider the plot given in Fig. 84 for the retractive force, measured at fixed length, against the absolute temperature for a hypothetical elastic substance. The slope at any temperature T gives the important quantity —(dS/dL)T,p according to Eq. (12) an increase in / with T at constant L shows immediately, therefore, that the entropy decreases with increase in length... 

For an elastic fiber such as a muscle fibril at constant temperature, the internal energy C7 is a function of three variables the entropy S, the volume V, and the length L. With the aid of the laws of thermodynamics, it is possible to show that... 

In a foregoing section, we mentioned that field forces (e,g., of the electric or elastic field) can cause an interface to move. If they are large enough so that inherent counterforces (such as interface tension or friction) do not bring the boundary to a stop, the interface motion would continue and eventually become uniform. In this section, however, we are primarily concerned with boundary motions caused by chemical potential changes. From irreversible thermodynamics, we know that the dissipated Gibbs energy of the discontinuous system is T-ab, where crb here is the entropy production (see Section 4.2). Since dG/dV = dG/dV = crb- T/ A < ), we have with Eqn. (4.8) at the boundary b... 

The second contribution to the steric interaction arises from the loss of configurational entropy of the chains on significant overlap. This effect is referred to as entropic, volume restriction, or elastic interaction, Gei. The latter increases very sharply with a decrease in h when the latter is less than 8. A schematic representation of the variation of Gmix, Gei, G, and Gj =G X + Gei + Ga) is given in Fig. 10. The total energy-distance curve shows only one minimum, at h 25, the depth of which depends on 5, R, and A. At a given R and A, G decreases with an increase in 5. With small particles and thick adsorbed layers (5 > 5 nm), G, becomes very small (approaches thermodynamic stability. This shows the importance of steric stabilization in controlling the flocculation of emulsions and suspensions. 

To understand robber elasticity we have to revisit some simple thermodynamics (the horror. the horror ). Let s start with the Helmholtz free energy of our piece of rubber, by which we mean that we are considering the free energy at constant temperature and volume (go to the review at the start of Chapter 10 if you ve also forgotten this stuff). If E is the internal energy (the sum of the potential and kinetic energies of all the particles in the system) and 5 the entropy, then (Equation 13-26) ... 

The aim of the thermodynamic treatment is to relate the elastic force opposing the deformation of the elastomer to changes in energy and entropy occurring during the process. 

The entropy of a network-solvent system will increase because of the tendency of the solvent molecules to disperse in the network. This is in analogy to thermodynamics of the dissolution process of macromolecules in a solvent. In reality, it is necessary to take into consideration the additional effect of interaction between polymer segments and solvent molecules, e.g., by introducing an interaction parameter. The dilation gives rise to an elastic response from the network chains which will oppose the tendency for dilation. 

---