Polymers adsorbed

Fig. XI-4. Schematic diagram of the structure of an adsorbed polymer chain. Segments are distributed into trains directly attached to the surface and loops and tails extending into solution.

A considerable number of experimental extensions have been developed in recent years. Luckliam et al [5] and Dan [ ] review examples of dynamic measurements in the SFA. Studying the visco-elastic response of surfactant films [ ] or adsorbed polymers [7, 9] promises to yield new insights into molecular mechanisms of frictional energy loss in boundary-lubricated systems [28, 70]. 

Luckham P F and Manimaaran S 1997 Investigating adsorbed polymer layer behaviour using dynamic surface forces apparatuses—a review Adv. Coiioid interface Sc/. 73 1 -46... 

Dhinojwala A and Granick S 1997 Surface forces In the tapping mode solvent permeability and hydrodynamic thickness of adsorbed polymer brushes Macromoiecuies 30 1079-85... 

In many colloidal systems, both in practice and in model studies, soluble polymers are used to control the particle interactions and the suspension stability. Here we distinguish tliree scenarios interactions between particles bearing a grafted polymer layer, forces due to the presence of non-adsorbing polymers in solution, and finally the interactions due to adsorbing polymer chains. Although these cases are discussed separately here, in practice more than one mechanism may be in operation for a given sample. 

The second case involves non-adsorbing polymer chains in solution. It was realized by Asakura aird Oosawa (AO) [50] aird separately by Vrij [51] tlrat tlrese chains will give rise to air effective attraction between colloidal particles. This is kirowir as depletion attraction (see figure C2.6.4. We will summarize tire AO tlreory to explain tlris. 

Finally, we briefly mention interactions due to adsorbing polymers. Block copolymers, witli one block strongly adsorbing to tire particles, have already been mentioned above. Flere, we focus on homopolymers tliat adsorb moderately strongly to tire particles. If tliis can be done such tliat a high surface coverage is achieved, tire adsorbed polymer layer may again produce a steric stabilization between tire particles. 

In section C2.6.4.3 it was shown how tlie addition of non-adsorbing polymer chains induces a depletion attraction between colloidal particles. If sufficient polymer is added, tliese attractions can be strong enough to induce a phase separation of tire colloidal particles. An early application of tliis was tire creaming of mbber latex [93]. 

Vincent B, Edwards J, Emmett S and Greet R 1988 Phase separation in dispersions of weakly-interacting particles in solutions of non-adsorbing polymers Colloid Surf. 31 267-98... 

Fig. 4. (a) Polymer bridging between particles and (b), particle stabilization by adsorbed polymer (32). 

The polymers exist in saline solution as tightly coiled chains and are readily adsorbed owing to relatively low solubiUty in hard water. Subsequent injection of soft, low salinity water uncoils the adsorbed polymer chains increasing water viscosity and reducing rock permeabiUty. This technology could also be used to reduce the permeabiUty of thief 2ones adjacent to injection wells. However, mechanical isolation of these 2ones may be necessary for cost-effective treatments. 

Two kinds of barriers are important for two-phase emulsions the electric double layer and steric repulsion from adsorbed polymers. An ionic surfactant adsorbed at the interface of an oil droplet in water orients the polar group toward the water. The counterions of the surfactant form a diffuse cloud reaching out into the continuous phase, the electric double layer. When the counterions start overlapping at the approach of two droplets, a repulsion force is experienced. The repulsion from the electric double layer is famous because it played a decisive role in the theory for colloidal stabiUty that is called DLVO, after its originators Derjaguin, Landau, Vervey, and Overbeek (14,15). The theory provided substantial progress in the understanding of colloidal stabihty, and its treatment dominated the colloid science Hterature for several decades. 

Ruths and Granick [95] have studied the self-adhesion of several monolayers and adsorbed polymers onto mica. For loose-packed monolayers, the adhesion, in excess of a constant value observed at low rate, increased as a power law with the square root of the separation rate. In the case of adsorbed diblocks, the excess adhesion increased linearly with logarithmic separation rate. The time effects were ascribed to interdigitation and interdiffusion between the contacting layers. 

While the static aspects of the adsorption of single chains at walls have been studied for a long time [2], the dynamic properties of adsorbed polymers have received much less attention [30-32]. Most work considers the kinetics of either adsorption or desorption of polymers at a solid surface [31], or the... 

Fig. 33(a,b) shows a series of snapshot pietures as a result of a eomputer experiment probing the kineties of dewetting. The loeal darkness of eaeh snapshot indieates the loeal eoverage of the substrate surfaee. Coverage fluetuations (white spots) appear rather early and get rapidly amplified. The substrate regions, eovered with polymer, have very irregular surfaee initially and are eonneeted with many weak links later, these hnks disappear, and the droplets of adsorbed polymer eompaetify, a pattern similar to spinodal deeomposition. 

A very similar effect of the surface concentration on the conformation of adsorbed macromolecules was observed by Cohen Stuart et al. [25] who studied the diffusion of the polystyrene latex particles in aqueous solutions of PEO by photon-correlation spectroscopy. The thickness of the hydrodynamic layer 8 (nm) calculated from the loss of the particle diffusivity was low at low coverage but showed a steep increase as the adsorbed amount exceeded a certain threshold. Concretely, 8 increased from 40 to 170 nm when the surface concentration of PEO rose from 1.0 to 1.5 mg/m2. This character of the dependence is consistent with the calculations made by the authors [25] according to the theory developed by Scheutjens and Fleer [10,12] which predicts a similar variation of the hydrodynamic layer thickness of adsorbed polymer with coverage. The dominant contribution to this thickness comes from long tails which extend far into the solution. 

It is precisely the loosening of a portion of polymer to which the authors of [47] attribute the observed decrease of viscosity when small quantities of filler are added. In their opinion, the filler particles added to the polymer melt tend to form a double shell (the inner one characterized by high density and a looser outer one) around themselves. The viscosity diminishes until so much filler is added that the entire polymer gets involved in the boundary layer. On further increase of filler content, the boundary layers on the new particles will be formed on account of the already loosened regions of the polymeric matrix. Finally, the layers on all particles become dense and the viscosity rises sharply after that the particle with adsorbed polymer will exhibit the usual hydrodynamic drag. 

FIG. 9 Schematic illustration of adsorption of poly(styrenesulfonate) on an oppositely charged surface. For an amphiphile surface in pure water or in simple electrolyte solutions, dissociation of charged groups leads to buildup of a classical double layer, (a) In the initial stage of adsorption, the polymer forms stoichiometric ion pairs and the layer becomes electroneutral, (b) At higher polyion concentrations, a process of restructuring of the adsorbed polymer builds a new double layer by additional binding of the polymer. 

A non-adsorbing polymer in solution can also destabilise a dispersion through a mechanism called depletion flocculation. When polymer molecules do not interact favourably with the particle surfaces from an enthal-pic perspective, they are repelled from the surface regions due to entropic reasons. A depletion zone around the particles is created which has a lower average polymer concentration than the bulk solution. The osmotic... 

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