Role of the Hydrophilic Latex Particle Surface in Water Diffusion into Films from Waterborne Polymer Colloids.

The diffusion mechanism and growth of large-scale domains during the immersion of latex films in water have been thoroughly investigated with scattering techniques in a combination with the gravimetric method. Latex dispersions for film formation studies had identical main monomer compositions and only differ in the hydrophilic comonomers that result in distinct "hairy" layer structures of the particles. The major effects of the presence and the structure of the surface layers were identified: (1) Introducing the hydrophilic surface layer in the binder structure results in a more uniform penetration of water and a reduction in the water domain growth. (2) The nature of the particle shell defines the rate of the formation of the first hydration layer and the beginning of the large cluster formation. Poly(acrylamide) in the particle shell promotes the formation of the homogeneously swollen film and slows down the development of water "pockets." Poly(acrylic acid) leads to a more heterogeneous material and accelerates water uptake and cluster growth. (3) The thickness of the particle hairy layer regulates the thickness of the interstitials in the dry film and the number of the chemical groups involved in H-bonding with water molecules without a cluster formation. The amount of water that was absorbed before large domains start evolving increased with the growth of the particle shell thickness.

Superviscosity and electroviscous effects at an electrode/aqueous electrolyte interface: an atomic force microscope study.

Several authors observed in the past a larger than twofold increase in viscosity of organic liquids under the influence of an electric field of the order of 10(6) V/m. This was called electro viscous effect (EVE). Significantly higher electric fields, of up to 10(8)-10(9) V/m, arise in the electric double layer in solutions close to an electrode. Therefore, the viscosity can be expected to increase at strongly charged liquid-solid interfaces. In more recent years, it was also observed that even in the absence of an externally controlled electric field the viscosity of water can be up to 10(7) times higher close to a hydrophilic surface than in the bulk ("hydrophilic forces"). Here, we present electrochemical atomic force microscopy (EC-AFM) measurements by which we can overcome the critical threshold of the electric field H=10(6) V/m by the control of the potentials applied to both a conducting sample and a conducting tip immersed in solution. Using the EC-AFM, we have investigated for the first time the EVE in an aqueous electrolyte. We can show that by controlling the applied potential, we can control the viscosity and the thickness of the super viscous liquid layer close to the solid interface. Using this technique, we are further able to separate effects on viscosity induced by the hydrophilicity of the surfaces, by the strong nanoconfinement of the liquid between tip and surface, and by the applied electric field.

Influence of wettability and surface charge on the interaction between an aqueous electrolyte solution and a solid surface.

The hydrodynamic drainage force of a Newtonian aqueous electrolyte solution squeezed between two surfaces of different wettability was measured using the AFM colloidal probe technique. The surface hydrophobicity, roughness, polarity and approach velocity, and thus the shearing rate of the liquid, were controlled. A direct relationship between the mobility of the aqueous electrolyte solution close to the surfaces and the hydrophobicity of the surfaces was not established. We predict that the mobility of the liquid depends in a more complex fashion on the polarity and charge of the surfaces and on the properties of the electrolyte.