Surface charge polymer adsorption

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. 

When a polyelectrolyte adsorbs on an oppositely charged surface the adsorbed amount compensates, or slightly over-compensates, the surface charge [6], Adsorption of cationic polymers continues even after the zeta potential is reversed [7], This is the case for cationic starch. 

The process of adsorption of polyelectrolytes on solid surfaces has been intensively studied because of its importance in technology, including steric stabilization of colloid particles [3,4]. This process has attracted increasing attention because of the recently developed, sophisticated use of polyelectrolyte adsorption alternate layer-by-layer adsorption [7] and stabilization of surfactant monolayers at the air-water interface [26], Surface forces measurement has been performed to study the adsorption process of a negatively charged polymer, poly(styrene sulfonate) (PSS), on a cationic monolayer of fluorocarbon ammonium amphiphilic 1 (Fig. 7) [27],... 

Plasmid DNA can be complexed electrostatically with cationic polymers. These complexes can be used for gene transfer [241]. Like the complexes of DNA with cationic lipids these complexes adhere to the cell surface with their cationic surface charges. Thereafter, they are internalized, presumably by adsorptive endocytosis. 

In the presence of divalent ions, apart from charge screening, adsorption can be modified due to additional factors arising from specific interactions of the divalent ions with the polymer and the surface. In this case, adsorption of calcium on the Si02 surface (15, 18) not only reduces the surface charge but can also... 

The adsorption of xanthan is increased by calcium but to a less extent than that for HP AM. The increased adsorption seems to be due mainly to the effects of screening of polymer and surface charges by calcium, and the maximum adsorption density is equivalent to that induced by monovalent ions. 

The ionic strength of the solution also significantly influences polyelectrolyte adsorption. In general, the higher the ionic strength of the medium, the less extended and the more coiled the polymer conformation becomes (due to preferential interaction with counter ions in solution rather than with other segments of the polymer chain). The coiled polymer becomes more accessible to the internal porous structure and adsorption is increased. However, for the same reason, it is less influential on the surface charge. 

Figure 6.8 Illustration of colloid-templated nanoparticle assemblies. The process involves the layer-by-layer adsorption of charged polymers and oppositely charged nanoparticles onto the surfaces of the colloidal template. The colloidal core particles may then be removed to generate a hollow sphere of nanoparticles, held together by electrostatic interactions with the linear polymer glue ...

Fabrication of organic thin films based on sponfaneous molecular assembly has been considered as one of fhe powerful approaches to create novel supramolecular systems. In this context, multilayer films were fabricated by layer-by-layer electrostatic deposition techniques based on the electrostatic interaction between dsDNA and the positively charged polymer poly(diallyldimethylammonium chloride) (PDDA) on GC surfaces. A uniform assembly of PDDA/DNA multilayer films was achieved, based on the adsorption of the negatively charged DNA molecules on the positively charged substrate [55]. 

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