Polymer fluids integral equation approaches

Over the p t several years we and our collaborators have pursued a continuous space liquid state approach to developing a computationally convenient microscopic theory of the equilibrium properties of polymeric systems. Integral equations method [5-7], now widely employed to understand structure, thermodynamics and phase transitions in atomic, colloidal, and small molecule fluids, have been generalized to treat macromolecular materials. The purpose of this paper is to provide the first comprehensive review of this work referred to collectively as Polymer Reference Interaction Site Model (PRISM) theory. A few new results on polymer alloys are also presented. Besides providing a unified description of the equilibrium properties of the polymer liquid phase, the integral equation approach can be combined with density functional and/or other methods to treat a variety of inhomogeneous fluid and solid problems. 

Finally, we mention that very recently three other integral equation approaches to treating polymer systems have been proposed. Chiew [104] has used the particle-particle perspective to develop theories of the intermolecular structure and thermodynamics of short chain fluids and mixtures. Lipson [105] has employed the Born-Green-Yvon (BGY) integral equation approach with the Kirkwood superposition approximation to treat compressible fluids and blends. Initial work with the BGY-based theory has considered lattice models and only thermodynamics, but in principle this approach can be applied to compute structural properties and treat continuum fluid models. Most recently, Gan and Eu employed a Kirkwood hierarchy approximation to construct a self-consistent integral equation theory of intramolecular and intermolecular correlations [106]. There are many differences between these integral equation approaches and PRISM theory which will be discussed in a future review [107]. 

There has been an explosive growth, particularly over the past couple of years, in developing continuum space integral equation theories for chain molecule and polymer fluids that are not based on the RISM formalism. There are at least three distinct classes of new theories. Our goal is to briefly summarize the various approaches and cite relevant references. A more detailed description of the technical aspects of the various theories, and the distinctive similarities and differences between them, will be the subject of a future review. We also point out that much progress has recently been made in developing statistical thermodynamic theories of sophisticated polymer lattice models by Freed and co-workers, and continuum polymer fluids by Hall and coworkers. Description of these advances are beyond the scope of this chapter. 

As a general comment on the recent polymer integral equation work, we note that applications to date have focused primarily on the structure (intra- and intermolecular) and equation of state (based on a virial or free energy route) of the simple hard core, tangent jointed chain model of polymer solutions and melts. How tractable and generalizable the various approaches are for treating semiflexible and/or atomistic models of macromolecular fluids is unclear for most theories. Little, or no, work has... 

Mitra et al. (1998) employed NSGA (Srinivas and Deb, 1994) to optimize the operation of an industrial nylon 6 semibatch reactor. The two objectives considered in this study were the minimization of the total reaction time and the concentration of the undesirable cyclic dimer in the polymer produced. The problem involves two equality constraints one to ensure a desired degree of polymerization in the product and the other, to ensure a desired value of the monomer conversion. The former was handled using a penalty function approach whereas the latter was used as a stopping criterion for the integration of the model equations. The decision variables were the vapor release rate history from the semibatch reactor and the jacket fluid temperature. It is important to note that the former variable is a function of time. Therefore, to encode it properly as a sequence of variables, the continuous rate history was discretized into several equally-spaced time points, with the first of these selected randomly between the two (original) bounds, and the rest selected randomly over smaller bounds around the previous generated value (so as... 

Other Constitutive Modei Descriptions. The above work describes a relatively simple way to think of nonlinear viscoelasticity, viz, as a sort of time-dependent elasticity. In solid polymers, it is important to consider compressibility issues that do not exist for the viscoelastic fluids discussed earlier. In this penultimate section of the article, other approaches to nonlinear viscoelasticity are discussed, hopefully not abandoning all simplicity. The development of nonlinear viscoelastic constitutive equations is a very sophisticated field that we will not even attempt to survey completely. One reason is that the most general constitutive equations that are of the multiple integral forms are cumbersome to use in practical applications. Also, the experimental task required to obtain the material parameters for the general constitutive models is fairly daunting. In addition, computationally, these can be difficult to handle, or are very CPU-time intensive. In the next sections, a class of single-integral nonlinear constitutive laws that are referred to as reduced time or material clock-type models is disscused. Where there has been some evaluation of the models, these are examined as well. 

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