Thermodynamics, polymer phase separations

Fundamental aspects of coacervation have been thoroughly covered for some time through the classical studies of Bungenberg de Jong and Kruyt for ionic systems, and by Dobry and Boyer-Kawenoki for non-ionic systems. The basic thermodynamic conditions for polymer-solvent interactions and polymer phase separation have been nicely described by Flory. In the following, polymer phase separation processes will be briefly considered from mechanistic and thermodynamic points of view. 

Exciplex states only exist at the interface between the two dissimilar polymers in the blend. Reducing the density of these interfaces in the polymer blend is expected to reduce the amount of exciplex observed. For example, annealing mobilizes the polymers and causes the film to move closer to thermodynamic equilibrium, i.e. the two polymers phase separate and the density of heterojunction sites decreases. Indeed, we observe that the amount of exciplex emission is reduced by the annealing treatment [30]. 

Many aspects of the formation of symmetric or asymmetric membranes can be rationalized by applying the basic thermodynamic and kinetic relations of phase separation. There are, however, other parameters-such as surface tension, polymer relaxation, sol and gel structures-which are not directly related to the thermodynamics of phase separation but which will have a strong effect on membrane structures and properties. A mathematical treatment of the formation of porous structures is difficult. But many aspects of membrane structures and the effect of various preparation parameters Can be qualitatively interpreted. 

With moderate compatibility, intermediate and complex phase behavior results. Thus IPNs with dispersed phase domains have been reported ranging from a few micrometers (the largest) to a few hundred nanometers (intermediate) to those without a resolvable domain structure (complete mixing). With highly incompatible polymers, on the other hand, the thermodynamics of phase separation is so powerful that it occurs before it can be prevented by cross-linking. 

This chapter summarizes the thermodynamics of multicomponent polymer systems, with special emphasis on polymer blends and mixtures. After a brief introduction of the relevant thermodynamic principles - laws of thermodynamics, definitions, and interrelations of thermodynamic variables and potentials - selected theories of liquid and polymer mixtures are provided Specifically, both lattice theories (such as the Hory-Huggins model. Equation of State theories, and the gas-lattice models) and ojf-lattice theories (such as the strong interaction model, heat of mixing approaches, and solubility parameter models) are discussed and compared. Model parameters are also tabulated for the each theory for common or representative polymer blends. In the second half of this chapter, the thermodynamics of phase separation are discussed, and experimental methods - for determining phase diagrams or for quantifying the theoretical model parameters - are mentioned. 

Using thermal analytical techniques, the range over which a polymer melts can readily be defined for various thermal histories, i.e. the rate of heating, the crystallization temperature, etc. Thermal history has an important ect since the melting point is determined by kinetic parameters and the thermodynamics of phase separation, and is not a unique parameter of the crystalline polymer. 

Ronca G, Russell TP (1985) Thermodynamics of phase separation in polymer mixtures. 

Phase separation can emerge spontaneously in thin films of polymer blend, and it is this thermodynamically driven phase-separation process that produces the patterning of thin polymer blend films. It can be induced by several parameters, each with critical values, including (i) the ratio between the components [10,22] (ii) the demixing temperature [12] and (iii) the chemical nature of the solvent. 

In recent years, a number of systems have been examined that also exhibit a lower critical solution temperature (LCST), as shown at the top of Figure 7.1. Here, a more unusual thermodynamic property is exhibited when the polymer phase separates from the solvent after being heated. (One might question the nomenclature the puts die LCST above the UCST, but that is the accepted definition.) LCSTs are more difficult to observe experimentally because they often lie well above the normal boiling points of the solvents. 

The fundamentals of the phase inversion process have been detailed in various publications and reviews and will be only briefly discussed here. ° The thermodynamics of phase separation follow the relationships established for polymer solvent mixtures and generally applied to temperature changes however, the same relationships also apply to nonsolvent introduction. In essence, the governing equations involve the free energy of mixing. 

There are several excellent books available which discuss polymer blends in general, including the thermodynamics of phase separation. The interested reader is referred to any of those texts to gain additional insights into polymer blends. A good reference to learn more about high temperature... 

In Chap. 8 we discuss the thermodynamics of polymer solutions, specifically with respect to phase separation and osmotic pressure. We shall devote considerable attention to statistical models to describe both the entropy and the enthalpy of mixtures. Of particular interest is the idea that the thermodynamic... 

The title of this chapter is somewhat misleading. In one sense it is too broad, in another sense too restrictive. We shall really discuss in detail only the phase separation and osmostic pressure of polymer solutions a variety of other thermodynamic phenomena are ignored. In this regard the chapter title would better read Some aspects of. . . . Throughout this volume only a small part of what might be said about any topic is actually presented, so this modifying phrase is taken to be understood and is omitted. 

Thermodynamics and kinetics of phase separation of polymer mixtures have benefited greatly from theories of spinodal decomposition and of classical nucleation. In fact, the best documented tests of the theory of spinodal decomposition have been performed on polymer mixtures. 

Compatibility. Clear definition of compatibility is rather difficult. Compatibility has been defined as the ability of two or more materials to exist in close and permanent association for an indefinite period without phase separation and without adverse effect of one on the other [28]. On the other hand, compatibility is easily recognized in solvent-borne adhesives as a homogeneous blend of materials without phase separation. Normally, compatibility is understood as a clear transparent mixture of a resin with a given polymer. But, compatibility is a more complex thermodynamic phenomenon which can be evaluated from specific... 

The flow behavior of the polymer blends is quite complex, influenced by the equilibrium thermodynamic, dynamics of phase separation, morphology, and flow geometry [2]. The flow properties of a two phase blend of incompatible polymers are determined by the properties of the component, that is the continuous phase while adding a low-viscosity component to a high-viscosity component melt. As long as the latter forms a continuous phase, the viscosity of the blend remains high. As soon as the phase inversion [2] occurs, the viscosity of the blend falls sharply, even with a relatively low content of low-viscosity component. Therefore, the S-shaped concentration dependence of the viscosity of blend of incompatible polymers is an indication of phase inversion. The temperature dependence of the viscosity of blends is determined by the viscous flow of the dispersion medium, which is affected by the presence of a second component. 

The term compatibility is used extensively in the blend literature and is used synonymously with the term miscibility in a thermodynamic sense. Compatible polymers are polymer mixtures that do not exhibit gross symptoms of phase separation when blended or polymer mixtures that have desirable chemical properties when blended. However, in a technological sense, the former is used to characterize the ease of fabrication or the properties of the two polymers in the blend [3-5]. 

The formation mechanism of structure of the crosslinked copolymer in the presence of solvents described on the basis of the Flory-Huggins theory of polymer solutions has been considered by Dusek [1,2]. In accordance with the proposed thermodynamic model [3], the main factors affecting phase separation in the course of heterophase crosslinking polymerization are the thermodynamic quality of the solvent determined by Huggins constant x for the polymer-solvent system and the quantity of the crosslinking agent introduced (polyvinyl comonomers). The theory makes it possible to determine the critical degree of copolymerization at which phase separation takes place. The study of this phenomenon is complex also because the comonomers act as diluents. 

The mechanism of phase separation proposed here (and also observed experimentally) involves the formation in the first stage of polymer blanks1, the globules size depends on the initial comonomers and the copolymerization conditions. In the case of slow phase separation proceeding near the thermodynamic equilibrium... 

A detailed description of AA, BB, CC step-growth copolymerization with phase separation is an involved task. Generally, the system we are attempting to model is a polymerization which proceeds homogeneously until some critical point when phase separation occurs into what we will call hard and soft domains. Each chemical species present is assumed to distribute itself between the two phases at the instant of phase separation as dictated by equilibrium thermodynamics. The polymerization proceeds now in the separate domains, perhaps at differen-rates. The monomers continue to distribute themselves between the phases, according to thermodynamic dictates, insofar as the time scales of diffusion and reaction will allow. Newly-formed polymer goes to one or the other phase, also dictated by the thermodynamic preference of its built-in chain micro — architecture. 

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