Neutral polymers, adsorption

Neutral polymers Adsorption on capillary wall Reduction of EOF and solute adsorption... 

Radeva Ts, Netzel J, Petkanchin I. Stoylov S. Electro-optic study of neutral polymer adsorption on mica. J Colloid Interface Sci 1993 160 493-495. 

Adsorption of macromolecules has been widely investigated both theoretically [9—12] and experimentally [13 -17]. In this paper our purpose was to analyze the probable structures of polymeric stationary phases, so we shall not go into complicated mathematical models but instead consider the main features of the phenomenon. The current state of the art was comprehensively summarized by Fleer and Lyklema [18]. According to them, the reversible adsorption of macromolecules and the structure of adsorbed layers is governed by a subtle balance between energetic and entropic factors. For neutral polymers, the simplest situation, already four contributor factors must be distinguished ... 

In the following paper, the possibility of equilibration of the primarily adsorbed portions of polymer was analyzed [20]. The surface coupling constant (k0) was introduced to characterize the polymer-surface interaction. The constant k0 includes an electrostatic interaction term, thus being k0 > 1 for polyelectrolytes and k0 1 for neutral polymers. It was found that, theoretically, the adsorption characteristics do not depend on the equilibration processes for k0 > 1. In contrast, for neutral polymers (k0 < 1), the difference between the equilibrium and non-equilibrium modes could be considerable. As more polymer is adsorbed, excluded-volume effects will swell out the loops of the adsorbate, so that the mutual reorientation of the polymer chains occurs. 

The chemical adsorption of a relatively high molecular weight neutral polymer (poly(succinimide), M = 13000) on aminopropyl-Vydac 101 TP silica gel was applied by Alpert [47, 48] to prepare a reactive composite support for use in cation-exchange [47] and hydrophobic-interaction [48] chromatography of pro-... 

In fact this "unhydrolyzed" polyacrylamide sample is slightly charged and its low polyectrolyte character is confirmed by a slight difference of red values at pH 7 and 5, for salt free solutions. A really neutral polymer should be necessary to differentiate low effects of electrostatic interactions from non ionic interactions. coordination binding at low pH and hydrogen bonds at pH 7. Nevertheless, at this pH, the adsorption of the chain on Al(0H)3 aggregates can probably be considered as the main origin of the loss of viscosity. 

If only electrostatic effects are responsible for polymer adsorption and flocculation, our results can be explained according to the same scheme as that used by Furusawa et Al.(20) to interprete the destabilization of negatively charged latex by a cationic polymer. In a first step, the adsorption of the polymer leads to the neutralization of the particles which are no more stabilized by electrostatic repulsions and there is flocculation (we have not studied this step since in our experiments polymer was always in large excess with respect to Al(0H)3). In a second step the adsorption inverses the charge and (we have indeed measured by... 

For h < 26, the situation is much more complex. One not only needs to know 4>(z) for each layer, but how 4>(z) changes as the two particles approach, i.e. 4>(z,h) this may well depend on the time-scale of the approach, i.e. the equilibrium path may not be followed. Scheutjens and Fleer (25) in an extension of their model for polymer adsorption have analysed the situation for two interacting uncharged parallel, flat plates carrying adsorbed, neutral homopolymer, interacting under equilibrium conditions. Only a semi-quantitative picture will be presented here. 

Fig. 4.16 provides an illustration of the adsorption of a neutral polymer, polyvinyl alcohol, on a polar surface, and the resulting effects on the double layer properties. Adsorption of anionic polymers on negative surfaces - especially in the presence of Ca2+ or Mg2+ which may act as coordinating links between the surface and functional groups of the polymer - is not uncommon (Tipping and Cooke, 1982). 

Alkali compounds are used in the Surtek process to reduce the interfacial tension between the oil phase and the aqueous phase. In addition, an alkaline agent neutralizes rock and clay surfaces and reduces the amount of exchangeable calcium and magnesium ions from the soil surface. Both of these functions reduce surfactant and polymer adsorption into the soil matrix. 

Synthetic polymers are widely applied to modify the surface properties of materials, and their adsorption mechanism is very different from small ions or molecules discussed in previous sections. Moreover, special methods are applied to study polymer adsorption, thus, polymer adsorption became a separate branch of colloid chemistry. Polymers that carry ionizable groups are referred to as polyelectrolytes. Their adsorption behavior is more sensitive to surface charging than adsorption of neutral polymers. Polyelectrolytes are strong or weak electrolytes, and the dissociation degree of weak polyelectrolytes is a function of the pH. The small counterions form a diffuse layer similar to that formed around a micelle of ionic surfactant. 

For neutral polymers adsorbing at a bare surface, this is all there is. Hence initial rates of adsorption from dilute solutions satisfy the simple equation... 

The neutralized polymer is more hydrophilic than its unneutralized counterpart, and the resulting enhanced compatibility with water would be expected to diminish the driving force for adsorption at the oil-water interface. The emulsion instability at higher pH values for systems containing 0.2% polymer can probably be explained by depletion of hydrophobe at the interface due to the enhanced hydrophilicity of the polymer at these pH values. 

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