Polymer solutions interface

Adsorption of dispersants at the soHd—Hquid interface from solution is normally measured by changes in the concentration of the dispersant after adsorption has occurred, and plotted as an adsorption isotherm. A classification system of adsorption isotherms has been developed to identify the mechanisms that may be operating, such as monolayer vs multilayer adsorption, and chemisorption vs physical adsorption (8). For moderate to high mol wt polymeric dispersants, the low energy (equiUbrium) configurations of the adsorbed layer are typically about 3—30 nm thick. Normally, the adsorption is monolayer, since the thickness of the first layer significantly reduces attraction for a second layer, unless the polymer is very low mol wt or adsorbs by being nearly immiscible with the solvent. 

The terminal R groups can be aromatic or aliphatic. Typically, they are derivatives of monohydric phenoHc compounds including phenol and alkylated phenols, eg, /-butylphenol. In iaterfacial polymerization, bisphenol A and a monofunctional terminator are dissolved in aqueous caustic. Methylene chloride containing a phase-transfer catalyst is added. The two-phase system is stirred and phosgene is added. The bisphenol A salt reacts with the phosgene at the interface of the two solutions and the polymer "grows" into the methylene chloride. The sodium chloride by-product enters the aqueous phase. Chain length is controlled by the amount of monohydric terminator. The methylene chloride—polymer solution is separated from the aqueous brine-laden by-products. The facile separation of a pure polymer solution is the key to the interfacial process. The methylene chloride solvent is removed, and the polymer is isolated in the form of pellets, powder, or slurries. 

Later we will describe both oxidation and reduction processes that are in agreement with the electrochemically stimulated conformational relaxation (ESCR) model presented at the end of the chapter. In a neutral state, most of the conducting polymers are an amorphous cross-linked network (Fig. 3). The linear chains between cross-linking points have strong van der Waals intrachain and interchain interactions, giving a compact solid [Fig. 14(a)]. By oxidation of the neutral chains, electrons are extracted from the chains. At the polymer/solution interface, positive radical cations (polarons) accumulate along the polymeric chains. The same density of counter-ions accumulates on the solution side. 

After polarization to more anodic potentials than E the subsequent polymeric oxidation is not yet controlled by the conformational relaxa-tion-nucleation, and a uniform and flat oxidation front, under diffusion control, advances from the polymer/solution interface to the polymer/metal interface by polarization at potentials more anodic than o-A polarization to any more cathodic potential than Es promotes a closing and compaction of the polymeric structure in such a magnitude that extra energy is now required to open the structure (AHe is the energy needed to relax 1 mol of segments), before the oxidation can be completed by penetration of counter-ions from the solution the electrochemical reaction starts under conformational relaxation control. So AHC is the energy required to compact 1 mol of the polymeric structure by cathodic polarization. Taking... 

By comparing impedance results for polypyrrole in electrolyte-polymer-electrolyte and electrode-polymer-electrolyte systems, Des-louis et alm have shown that the charge-transfer resistance in the latter case can contain contributions from both interfaces. Charge-transfer resistances at the polymer/electrode interface were about five times higher than those at the polymer/solution interface. Thus the assignments made by Albery and Mount,203 and by Ren and Pickup145 are supported, with the caveat that only the primary source of the high-frequency semicircle was identified. Contributions from the polymer/solution interface, and possibly from the bulk, are probably responsible for the deviations from the theoretical expressions/45... 

On the other hand, Doblhofer218 has pointed out that since conducting polymer films are solvated and contain mobile ions, the potential drop occurs primarily at the metal/polymer interface. As with a redox polymer, electrons move across the film because of concentration gradients of oxidized and reduced sites, and redox processes involving solution species occur as bimolecular reactions with polymer redox sites at the polymer/solution interface. This model was found to be consistent with data for the reduction and oxidation of a variety of species at poly(7V-methylpyrrole). This polymer has a relatively low maximum conductivity (10-6 - 10 5 S cm"1) and was only partially oxidized in the mediation experiments, which may explain why it behaved more like a redox polymer than a typical conducting polymer. 

Deviation refractometers are the most commonly used. This version of the DRI measures the deflection in the location of a light beam on the surface of a photodiode by the difference in refractive index between the polymer solution and pure solvent. The Fresnel-type refractometers operate on the principle that the intensity of light reflected from a glass-liquid interface is dependent on the incident angle and the RI difference between the two phases. The deviation and Fresnel detectors typically have cell volumes of 5 to 10 pi, detection limits of about 5 x 10-6 refractive index units (RIU), and a range of 10 7 to 10 3 RIU.156 The deflection-type DRI is relatively insensitive to the buildup of contaminants on the sample cell and is therefore of special utility in laboratories that process large numbers of samples, such as industrial laboratories. 

A discussion of the charge transfer reaction on the polymer-modified electrode should consider not only the interaction of the mediator with the electrode and a solution species (as with chemically modified electrodes), but also the transport processes across the film. Let us assume that a solution species S reacts with the mediator Red/Ox couple as depicted in Fig. 5.32. Besides the simple charge transfer reaction with the mediator at the interface film/solution, we have also to include diffusion of species S in the polymer film (the diffusion coefficient DSp, which is usually much lower than in solution), and also charge propagation via immobilized redox centres in the film. This can formally be described by a diffusion coefficient Dp which is dependent on the concentration of the redox sites and their mutual distance (cf. Eq. (2.6.33). 

In the previous sections, we described the overall features of the heat-induced phase transition of neutral polymers in water and placed the phenomenon within the context of the general understanding of the temperature dependence of polymer solutions. We emphasised one of the characteristic features of thermally responsive polymers in water, namely their increased hydropho-bicity at elevated temperature, which can, in turn, cause coagulation and macroscopic phase separation. We noted also, that in order to circumvent this macroscopic event, polymer chemists have devised a number of routes to enhance the colloidal stability of neutral globules at elevated temperature by adjusting the properties of the particle-water interface. 

W. M. Reichert, J. T. Ives, P. A. Suci, and V. Hlady, Excitation of fluorescent emission from solutions at the surface of polymer thin-film waveguides An integrated optics technique for the sensing of fluorescence at the polymer/solution interface, Appl. Spectrosc. 41, 636-639... 

Then we address the dynamics of diblock copolymer melts. There we discuss the single chain dynamics, the collective dynamics as well as the dynamics of the interfaces in microphase separated systems. The next degree of complication is reached when we discuss the dynamic of gels (Chap. 6.3) and that of polymer aggregates like micelles or polymers with complex architecture such as stars and dendrimers. Chapter 6.5 addresses the first measurements on a rubbery electrolyte. Some new results on polymer solutions are discussed in Chap. 6.6 with particular emphasis on theta solvents and hydrodynamic screening. Chapter 6.7 finally addresses experiments that have been performed on biological macromolecules. 

Figure II. Initial mechanisms of phase inversion (I) polymer solution interface at zero time (II) initial depletion of solvent, inward contraction, and formation of the nodular layer (III) end of contraction and establishment of the nodular layer.

Morgan, P.W. 1965. Condensation Polymers by Interface and Solution Methods. Wiley, New York. Morgan, P.W. and Kwolek, S.L. 1959. The nylon rope trick. J. Chem. Ed., 36 182. 

Pearce E, Kwei TK (1992) In Noda 1, Rubingh D (eds) Polymer solutions, blends and interfaces. Elsevier, Amsterdam, pp 133-149... 

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