Effects of Light Dispersed Particles on the Stability of Dense Suspended Particles Against Sedimentation.

A novel method in which vesicular dispersions of the double-chain cationic surfactant DDAB (didodecyldimethylammonium bromide) stabilize suspensions of high density titania particles was recently presented (Yang, Y.-J; Corti, D.S.; Franses, E. I. Langmuir 2015, 31, 8802-8808). At high enough DDAB concentration, the vesicles form a close-packed structure, providing strong resistance to the sedimentation of the titania particles, while the dispersions remain highly shear-thinning with moderate limiting viscosities. Here, to elucidate the key factors of the mechanism by which vesicles or other nonsettling particles stabilize high density particles against sedimentation, we use Brownian dynamics simulations (BDS) to examine the sedimentation behavior of mixtures of "dense particles" that settle rapidly on their own and "light particles" that represent nonsettling "rigid vesicles". BDS confirm that for large enough values of the volume fraction ϕ2 of the light particles, the dense particles should remain suspended. The rheological behavior of the mixtures is also computed with BDS. The observed shear-thinning behavior of the light particle dispersion suggests that the suspensions of the dense particles are still flowable at high shear stresses. Furthermore, the local viscosity of light particles around the dense particles significantly increases with increasing ϕ2, particularly when the same gravitational force applied in the BDS is exerted on a dense particle. The arrangement of light particles around the moving dense particles is an important factor in determining the stability of the dense particles against sedimentation. The BDS results indicate that dispersions of nonsettling particles provide a general method for the stabilization against sedimentation of high density particles.

Use of Close-Packed Vesicular Dispersions to Stabilize Colloidal Particle Dispersions against Sedimentation.

For many applications of colloidal dispersions, the particles must be suspended for a long time. This is often accomplished by preventing agglomeration, which generates aggregates of increasing size. Nevertheless, many colloidal dispersions of dense particles may settle even without agglomeration. Preventing sedimentation without significantly increasing the bulk dispersion viscosity is difficult and has received little attention in the literature. However, settling can be drastically reduced through the novel use of close-packed vesicular dispersions at high enough concentrations, which are non-Newtonian shear-thinning fluids. Such dispersions have much higher viscosities at the low shear stresses "felt" by sedimenting colloidal particles than at the high shear stresses relevant to bulk dispersion flow. In a practical example, dense TiO2 nanoparticles which normally would settle rapidly can remain suspended for at least 6 months without any observable sedimentation when they are introduced into a close-packed vesicular dispersion, while the dispersion retains its flowability. Cryo-TEM images reveal that the vesicles in these dispersions are tightly close-packed. Dynamic light scattering and electrophoretic mobility data also confirm that the vesicles in such dispersions have very low mobilities.

Effect of sodium dodecylsulfate monomers and micelles on the stability of aqueous dispersions of titanium dioxide pigment nanoparticles against agglomeration and sedimentation.

HYPOTHESIS: As more sodium dodecylsulfate (SDS) monomers adsorb at the water/titanium dioxide (TiO2) nanoparticles interface, the particles become more stable against agglomeration and sediment more slowly. SDS micelles are not expected to adsorb on the particles and affect the stability against agglomeration or sedimentation. Since micelles are smaller than the 300 nm TiO2 nanoparticles studied, they may introduce depletion forces which may affect the dispersion stability. EXPERIMENTS AND MODELS: Sedimentation times were measured in water and in 100 mM NaCl for SDS concentrations from 0.1 to 200 mM. Adsorption densities of SDS and zeta potentials of particles were measured. Dynamic light scattering was used to measure average diameters of particles or particle agglomerates. Modeling of sedimentation/diffusion was done to predict sedimentation times of particles. Modeling of agglomeration rates was done to help predict sedimentation rates of clusters. FINDINGS: At SDS concentrations close to or above the cmc, up to 60 mM in water or 115 mM in 100 mM NaCl, the nanoparticles sediment most slowly without any agglomeration. At higher micelle concentration, SDS micelle depletion forces are very strong, causing fast flocculation, without coagulation. Then sedimentation occurs much faster. The effective micelle depletant size includes about 4 Debye lengths of the charged micelles or particles.