Bernard Cabane

Interparticle distances in flocs

Abstract Silica spheres dispersed in water are flocculated by adding macromolecules that adsorb on their surfaces. The resulting flocs are macroscopic, heterogenous aggregates of spheres between which cohesion is caused by the adsorbed polymer layes, Small-angle neutron scattering is used to measure the distances between spheres in a floc. According to the distribution of these distances, the structures of flocs fall into two classes: (1) aggregates in which the particles are in direct contact—these are tenuous, self-similar structures that resemble those derived from models bases on random collisions; (2) aggregates in which the particles are prevented from coming into direct contact—these structures show a very strong short-range order similar to that observed in a concentrated dispersion of spheres, yet at large scales their organization is dominated by heterogeneities in the density of the floc.

Growth of colloidal aggregates through polymer bridging

The stability of colloidal dispersions can be altered through the addition of adsorbing macromolecules. Adsorption of macromolecules on the particle surfaces results in a stepwise aggregation process. We consider the early destabilization steps for nanometric ceria particles dispersed in water. These steps have been characterized through light scattering; they are: i) finite multiplets involving one macromolecule and a small number of particles; ii) bridging between mul tiplets; iii) formation of three-dimensional network of bridges. Each stage can be obtained as an equilibrium state, provided there is an adequate balance of electrostatic repulsions and polymer-induced attractions. Altering this balance may push the system from one state into another, or it may change the structure within one state. For instance, multiplets may be pushed to bind more particles or spill them out, depending on the equilibrium length of bridge; gels may reject solvent and turn into flocs if the equilibrium length of bridges becomes shorter than the average distance between particles.

Short range order of silica particles bound through adsorbed polymer layers

Small angle neutron scattering was used to examine the organization of silica spheres which had been flocculated by various cationic copolymers. When the adsorbed polymers bound the spheres without compensating their surface charge, the resulting aggregates had a liquid-like short range order. When the polymers compensated for the surface charges, we found only tenuous aggregates with self-similar structures.

Osmotic compression of mixtures of polymers and particles

Aqueous dispersions of nanometric ceria particles have been concentrated through osmotic stress. Mixed dispersions of ceria with small adsorbing macromolecules of poly (vinylpyrrolidone) have been prepared by the same method. The osmotic pressure of pure ceria dispersions results from electrostatic repulsions between particles. The osmotic pressure of dispersions containing a non-saturating amount of PVP is the same as that of pure dispersions, and the colloidal stability is depressed with respect to the pure dispersions. The osmotic pressure of dispersions containing an excess of PVP is increased by the free macromolecules, and the colloidal stability is enhanced. The organization of particles in these dispersions has been examined by small-angle x-ray scattering and cryotransmission electron microscopy. In pure ceria dispersions and in saturated dispersions, a liquid-like short-range order was found; when the concentration is increased, this short-range order follows a three-dimensional swelling law. In dispersions containing a non-saturating amount of PVP, the structure shows an alternance of clusters and voids, and the separations of clusters follow an unusual one-dimensional swelling law.

Competition between ligands for Al2O3 in aqueous solution.

The adsorption of two classes of carboxylic ligands (i.e., aliphatic and aromatic small molecules), onto α-alumina nanoparticles was investigated. A new methodology was used whereby two molecules were simultaneously equilibrated with the inorganic material. A two-dimensional representation of the adsorption of the two complexing molecules enables us to differentiate between pairs of ligands with (i) independent adsorption on different sites of the alumina particles, (ii) competing adsorption on the same sites, or (iii) a mix thereof. Both the highest affinity ligands (tetracarboxylic acid, citric acid, and tiron), and the way they compete with lower affinity ligands have been identified. The combination of carbon skeleton and complexing groups required to produce the ligand of highest affinity at pH 5 has been recognized. In particular, the role of the OH in the α position of a carboxylic group and the role of the distance between two carboxylic groups are emphasized.