Flory polymer adsorption

The role of the solvent in polymer adsorption has been the subject of much discussion. For example, theories have made predictions about the effect of the polymer/solvent interaction (i.e. Flory Huggins x parameter) on adsorption. For many systems, x parameters had already been tabulated so that a number of adsorption studies focused attention on this parameter. In spite of much effort, available data are ambiguous, sometimes verifying and sometimes contradicting the trends predicted by theory. 

In addition to the solubility parameter model to treat SEC adsorption effects, an approach based on Flory-Huggins interaction parameters has also been proposed (24-27). For an excellent review of both mechanisms, see reference 28.- A general treatment of polymer adsorption onto chromatographic packings can be found in Belenkii and Vilenchik s recent book (29). 

To understand the behavior of polymers at interfaces, it is essential to gain a clear picture of then-behavior in solution first. Modem polymer solution studies were pioneered by Flory. Since then, there has been considerable effort to elucidate solution behavior of polymers and many models have been proposed. The theoretical treatment of polymer adsorption characteristics and conformation characteristics received considerable attention, mainly because of the significant applications. 

However, the modem experimental methods, in particular, an ellip-sometry and the neutron reflection [72], give the values of the adsorption layer thickness h neared to the sizes of the Flory ball in solution, h R that points on the volumetric character of the polymer adsorption but not on the plate one. 

The second contribution influencing polymer adsorption from solution is the Flory-Huggins interaction parameter between poljnner and solvent. Such an enthalpy of mixing term adds a contribution of X (t)2 z) — 4> ) to the interaction energy contribution, where 4) is the bulk solution concentration of the polymer (2) and, when approaches thermodynamically poor values, then the adsorbed amoimt of pol3mier increases significantly. Figure 5.13 shows experi-... 

In Chapter 3, the solution and surface properties of a relatively new class of material, namely, polymeric surfactants, are illustrated in some detail using Flory-Huggins theory and current polymer-adsorption theory. This is followed by a discussion of the phenomenon of steric stabilization of suspended particles and how it is affected by the detailed structure of the stabilizing polymeric species. It concludes with a discussion of the stabilization of emulsions by interfacial and bulk theological effects, and presents closing comments on multiple emulsions. 

The above discussion on the two components of should lead to a better understanding of physical adsorption. Theoretically, polymer adsorption(so) can be treated by the Scheutjens-Fleer (SF)(si) mean-field theory, the Monte Carlo (MC) method,( 2) or the scaling approach. (83) In Figure 10, two profiles are given for the cases of adsorption (x = 1) and depletion (x = 0) using the SF theory, where x is the Flory-Huggins interaction parameter(84) between a polymer and a solvent with respect to pure components. The polymer coil expands if X < 0.5 and contracts if x These two cases are referred to as good and poor solvents, respectively. From the volume fraction profile c )(z), we can calculate other adsorption parameters, such as F, the adsorbed amount ... 

In the polymer adsorption, m(z) is not a fixed imposed field, but it is affected by the accumulation of segments near the surface or it is a function of the segment volume fraction (p z). Therefore, the self-consistent field may be described by Eq. (6) according to an extended Flory-Huggins model ... 

The experimental thickness measurements may also be compared with theoretical results based on profiles generated by the S.F., Scheutjens Fleer, theory (11). For this calculation we use a value for xs °f 1 (net adsorption free energy), for x of 0.45 (experimental value of the Flory-Huggins parameter) and a polymer solution concentration of 200 ppm. Although the value for xs seems rather arbitrary it has been shown (10) that 6jj is insensitive to this parameter. 

The original treatment of this type of displacement isotherm was developed by Flory and Huggins separately, back in 1942. They developed the isotherm for adsorption of large molecules (polymers). However, applicability to small molecules (e.g., ions) displacing only few water molecules has been proved. 

SCFT today is one of the most commonly used tools in polymer science. SCFT is based on de Gennes-Edwards description of a polymer molecule as a flexible Gaussian chain combined with the Flory-Huggins "local" treatment of intermolecular interactions. Applications of SCFT include thermodynamics of block copolymers (Bates and Fredrickson, 1999 Matsen and Bates, 1996), adsorption of polymer chains on solid surfaces (Scheutjens and Fleer, 1979,1980), and calculation of interfacial tension in binary polymer blends compatibilized by block copolymers (Lyatskaya et al., 1996), among others. 

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