Flory—Huggins theory lattice model

Simulations [73] have recently provided some insights into the formal 5c —> 0 limit predicted by mean field lattice model theories of glass formation. While Monte Carlo estimates of x for a Flory-Huggins (FH) lattice model of a semifiexible polymer melt extrapolate to infinity near the ideal glass transition temperature Tq, where 5c extrapolates to zero, the values of 5c computed from GD theory are too low by roughly a constant compared to the simulation estimates, and this constant shift is suggested to be sufficient to prevent 5c from strictly vanishing [73, 74]. Hence, we can reasonably infer that 5 approaches a small, but nonzero asymptotic low temperature limit and that 5c similarly becomes critically small near Tq. The possibility of a constant... 

One early considered approach was to extend Flory-Huggins-like lattice models by introducing empty lattice sites (holes) so that the number of holes in the lattice is a measure of the density of the system. Density changes in the system are realized via a variation of the hole number. Equations of state based on this idea are, for example, the Lattice-Huid Theory firom Sanchez and Lacombe [4] and the Mean-Field Lattice-Gas theory firom Kleintjens and Koningsveld [5]. 

The lattice model that served as the basis for calculating ASj in the last section continues to characterize the Flory-Huggins theory in the development of an expression for AHj . Specifically, we are concerned with the change in enthalpy which occurs when one species is replaced by another in adjacent lattice sites. The situation can be represented in the notation of a chemical reaction ... 

In this section and the last, we have examined the lattice model of the Flory-Huggins theory for general expressions relating AHj and ASj to the composition of the mixture. The separate components can therefore be put together to give an expression for AGj as a function of temperature and composition ... 

The Flory-Huggins theory begins with a model for the polymer solution that visualizes the solution as a three-dimensional lattice of TV sites of equal volume. Each lattice site is able to accommodate either one solvent molecule or one polymer segment since both of these are assumed to be of equal volume. The polymer chains are assumed to be monodisperse and to consist of n segments each. Thus, if the solution contains TV, solvent molecules and TV2 solute (polymer) molecules, the total number of lattice sites is given by... 

Taking into account the modes in which the water can be sorbed in the resin, different models should be considered to describe the overall process. First, the ordinary dissolution of a substance in the polymer may be described by the Flory-Huggins theory which treats the random mixing of an unoriented polymer and a solvent by using the liquid lattice approach. If as is the penetrant external activity, vp the polymer volume fraction and the solvent-polymer interaction parameter, the relationship relating these variables in the case of polymer of infinite molecular weight is as follows ... 

The model of Marchetti et al. is based on the compressible lattice theory which Sanchez and Lacombe developed to apply to polymer-solvent systems which have variable levels of free volume [138-141], This theory is a ternary version of classic Flory-Huggins theory, with the third component in the polymer-solvent system being vacant lattice sites or holes . The key parameters in this theory which affect the polymer-solvent phase diagram are ... 

Several other studies have also been made in an attempt to account theoretically for the phase transition in terms different from those of the Flory-Huggins theory. Otake et al. [55] thus proposed a theoretical model that takes hydrophobic interaction into account in explaining the thermally induced discontinuous volume collapse of hydrogels. In addition, Prausnitz et al. [56] proposed a lattice model, an improvement of which was made to explain the swelling curves of gels consisting of /V,/V -methylenebis(acrylamide) (MBA)-crosslinked copolymers of AAm with [(methacrylamide)propyl]trimethyl-ammonium chloride (MAPTAC) [57],... 

Using the lattice model, the approximate value of W in the Boltzmann equation can be estimated. Two separate approaches to this appeared in 1942, one by P. J. Flory, the other by M. L. Huggins, and though they differed in detail, the approaches are usually combined and known as the Flory-Huggins theory. This gives the result for entropy of mixing of follows ... 

The randomly occupied lattice model of a polymer solution used in the Flory-Huggins theory is not a good model of a real polymer solution, particularly at low concentration. In reality, such a solution must consist of regions of pure solvent interspersed with locally concentrated domains of solvated polymer. 

Sanchez and Lacombe (1976) developed an equation of state for pure fluids that was later extended to mixtures (Lacombe and Sanchez, 1976). The Sanchez-Lacombe equation of state is based on hole theory and uses a random mixing expression for the attractive energy term. Random mixing means that the composition everywhere in the solution is equal to the overall composition, i.e., there are no local composition effects. Hole theory differs from the lattice model used in the Flory-Huggins theory because here the density of the mixture is allowed to vary by increasing the fraction of holes in the lattice. In the Flory-Huggins treatment every site is occupied by a solvent molecule or polymer segment. The Sanchez-Lacombe equation of state takes the form... 

To calculate AWm (the enthalpy of mixing) the polymer solution is approximated by a mixture of solvent molecules and polymer segments, and AW is estimated from the number of 1,2 contacts, as in Section 12.2.1. The terminology is somewhat different in the Flory-Huggins theory, however. A site in the liquid lattice is assumed to have z nearest neighbors and a line of reasoning similar to that developed above for the solubility parameter model leads to the expression... 

For polymers, x is usually defined on a per monomer basis or on the basis of a reference volume of order one monomer in size. However, x is usually not computed from formulas for van der Waals interactions, but is adjusted to obtain the best agreement between the Flory-Huggins theory and experimental data on the scattering or phase behavior of mixtures (Balsara 1996). In this fitting process, inaccuracies and ambiguities in the lattice model, as well as in the mean-field approximations used to obtain Eq. (2-28), are papered over, and contributions to the free energy from sources other than simple van der Waals interactions get lumped into the x parameter. The temperature dependences of x for polymeric mixtures are often fit to... 

Although the Flory-Huggins theory was derived from a lattice model in which units of polymer A and polymer B are-the same size (i.e., they each occupy a single lattice cell), the theory is readily generalized so that it can apply to realistic cases in which the volumes of monomers A and B are unequal ... 

Problem 3.2 Calculate, in terms of the lattice model of the Flory-Huggins theory, the number of segments per polystyrene molecule of molecular weight 290,000 dissolved in (a) toluene and (b) methyl ethyl ketone (MEK) at 25°C. 

The deficiencies of the Flory-Huggins theory result from the limitations both of the model and of the assumptions employed in its derivation. Thus, the use of a single type of lattice for pure solvent, pure polymer and their mixtures is clearly unrealistic since it requires that there is no volume change upon mixing. The method used in the model to calculate the total number of possible conformations of a polymer molecule in the lattice is also unrealistic since it does not exclude self-intersections of the chain. Moreover, the use of a mean-field approximation to facilitate this calculation, whereby it is assumed that the segments of the previously added polymer molecules are distributed uniformly in the lattice, is satisfactory only when the volume fraction (f>2 of polymer is high, as in relatively concentrated polymer solutions. 

In this section, we mention very briefly some recent theoretical developments, which go far beyond the simple Flory-Huggins theory. As was emphasized above, the Flory-Huggins theory suffers from two basic defects (i) Using a lattice model where polymers are represented as self-avoiding walks is a crude approximation, which neglects the disparity in size and shape of subunits of the two types of chain in a polymer blend, as well as packing constraints, specific interactions etc. (ii) Even within the realm of a lattice model, the statistical mechanics (involving approximations beyond the mean field approximation) is far too crude. 

The Flory-Huggins theory is in fact nothing more than a two-component polymer version of the simple lattice gas model introduced in section 2. We divide the free energy into an entropic part, which is assumed to take the simplest perfect gas form, while the enthalpic part is estimated using a typical mean-field assumption. 

Flory-Huggins theory (Flory, 1941, 1942, 1945 Huggins, 1941, 1942abc, 1958 Tompa, 1956 Volkenshtcin, 1959 Casassa, 1976, 1977) is based on a model of a rigid lattice of m cells, whose volume i i is commensurable to that of the LMWL molecule. The lattice with the coordination number u contains m2 macromolecules and m LMWL molecules. Each macromolecule is composed of z fragments (segments), each occupying one cell of the lattice ... 

The above-mentioned deficiencies of the Flory-Huggins theory can be alleviated, in part, by using the local-composition concept based on Guggenheim s quasichemical theory for the random mixing assumption and replacing lattice theory with an equation-of-state model (Prausnitz et al., 1986). More sophisticated models are available, such as the perturbed hard sphere chain (PHSC) and the statistical associating fluid theory (SAFT) (Caneba and Shi, 2002), but they are too mathematically sophisticated that they are impractical for subsequent computational efforts. 

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