Swelling and collapse of an adsorbed pH-responsive film-forming microgel measured by optical reflectometry and QCM.

The swelling and deswelling of a pH-responsive electrosterically stabilized poly[2-(diethylamino)ethyl methacrylate] microgel adsorbed to silica surfaces have been quantified using the techniques of optical reflectometry (OR) and quartz crystal microbalance (QCM). It is shown that by utilizing and comparing OR measurements performed on wafers with differing oxide layer thicknesses the adsorbed amount and film thickness of the adsorbed microgel in both the swollen and deswollen forms can be determined. Also, the kinetics of the transition can be followed, revealing that collapse is a slower process than swelling, and direct support is provided for the formation of a dense outer layer or skin during collapse that slows the deswelling process. It is shown that the adsorption of this low glass transition temperature film-forming microgel latex is robust to changes in pH after an initial swelling event which is responsible for desorption of a large and variable fraction of the initially adsorbed polymer. Subsequent deswelling and swelling of the adsorbed film indicates that adsorption to a surface greatly hinders the volumetric swelling capacity of the microgel film. In its swollen state the film is only 3-4 times thicker than the collapsed film, whereas for particles in bulk the volume increases by a factor of 20 upon protonation of the tertiary amine residues. QCM results show that even in the collapsed form the film contains a considerable amount of water. Further, the viscoelasticity of the deswollen film is similar to that of the swollen film, suggesting that the degree of cross-linking is the primary determinant of viscoelasticity.

Measurement of no-slip and slip boundary conditions in confined Newtonian fluids using atomic force microscopy.

We report measurements of slip length at smooth and rough hydrophilic silica surfaces, using the hydrodynamic force measurement atomic force microscope (AFM). There has been some debate in the literature as to whether the boundary condition between a solid and a wetting fluid is one of no-slip or partial-slip; in particular the results of Neto et al. (C. Neto, V. S. J. Craig and D. R. M. Williams, Eur. Phys. J. E, 2003, 12, S71-S74) and of Honig and Ducker (C. D. F. Honig and W. A. Ducker, Phys. Rev. Lett., 2007, 98, 028305) are inconsistent. Unexpectedly, the AFM cantilever geometry leads to a different measurement of hydrodynamic drainage force. Rectangular cantilevers give results consistent with a no-slip boundary condition on smooth and rough surfaces, while v-shaped cantilever measurements show variability and can produce a finding of apparent partial-slip, consistent with earlier results in the literature. Possible reasons for the discrepancy are discussed. Equilibrium force measurements show no cantilever shape dependence. We conclude that the appropriate boundary condition for aqueous solutions on smooth and nanoscale-rough hydrophilic surfaces is one of no-slip.

Roughness of microspheres for force measurements.

We have investigated the morphology and surface roughness of several commercially available microspheres to determine their suitability for force measurements using the atomic force microscope. The roughness varies considerably, depending on sphere size and material, ranging from nearly ideally flat up to micrometer-sized features. Because surface roughness significantly influences the magnitude and accuracy of measurement of surface forces, the results presented here should be helpful for colloid physicists and in particular for those performing force measurements.

Adsorption and desorption of polymer/surfactant mixtures at solid-liquid interfaces: substitution experiments.

The adsorption of mixtures of aqueous solutions of cationic hydroxyethylcellulose polymer JR400 and anionic surfactant, sodium dodecyl sulfate, using atomic force microscopy (AFM) has been studied. Samples with various compositions from different regions of the ternary phase diagram presented in our previous work were imaged by atomic force microscopy on freshly cleaved mica, and hydrophobically modified mica and silica in soft-contact mode. A series of "washing" (subsequent injection of compositions with gradually decreasing polymer/surfactant ratio) and "scratching" (mechanical agitation of the surface material with an AFM tip) experiments were performed. It was revealed that the morphology of the adsorbed layer altered in a manner following the changes in morphology in the bulk solution. These changes were evidenced in cluster formation in the layer. The results suggest that the influence of the surface was limited to the formation of the adsorbed layer where the local concentrations of polymer and surfactant were higher than those in the bulk. All further modifications were driven by changes in the mixture composition in bulk. Force measurements upon retraction reveal the formation of network structures within the surface aggregates that will greatly slow structural reequilibration.

Adsorption pattern of mixtures of trimethylammonium-modified hydroxyethylcellulose and sodium dodecyl sulfate at solid-liquid interfaces.

We studied mixtures of aqueous solutions of cationic hydroxyethylcellulose JR400 polymer and anionic sodium dodecyl sulfate using dynamic light scattering and atomic force microscopy (AFM). A ternary phase diagram was established showing three interesting realms of the polymer-surfactant-water mixture: a preprecipitation area of lowered viscosity (polymer excess) compared to the pure polymer solution, a postprecipitation area (resolubilization at surfactant excess), and highly diluted samples with a stoichiometrical surfactant-polymer ratio close to that of maximum precipitation. Samples with various compositions representing these areas were imaged by atomic force microscopy on mica and on hydrophobically modified silica in contact mode. A correlation between light scattering data concerning particle size and, more important, structuring in the bulk on one hand and AFM images on the other hand was observed. It was revealed that the influence of surface properties is of less importance for adsorption, compared to the influence of the mixture in the bulk, provided that the mixture is prepared prior to adsorption.

The influence of chain length and electrolyte on the adsorption kinetics of cationic surfactants at the silica-aqueous solution interface.

The equilibrium and kinetic aspects of the adsorption of alkyltrimethylammonium surfactants at the silica-aqueous solution interface have been investigated using optical reflectometry. The effect of added electrolyte, the length of the hydrocarbon chain, and of the counter- and co-ions has been elucidated. Increasing the length of the surfactant hydrocarbon chain results in the adsorption isotherm being displaced to lower concentrations. The adsorption kinetics indicate that above the cmc micelles are adsorbing directly to the surface and that as the chain length increases the hydrophobicity of the surfactant has a greater influence on the adsoption kinetics. While the addition of 10 mM KBr increases the CTAB maximal surface excess, there is no corresponding increase for the addition of 10 mM KCl to the CTAC system. This is attributed to the decreased binding efficiency of the chloride ion relative to the bromide ion. Variations in the co-ion species (Li, Na, K) have little effect on the adsorption rate and surface excess of CTAC up to a bulk electrolyte concentration of 10 mM. However, the rate of adsorption is increased in the presence of electrolyte. Slow secondary adsorption is seen over a range of concentrations for CTAC in the absence of electrolyte and importantly in the presence of LiCl; the origin of this slow adsorption is attributed to a structural barrier to adsorption.

Mechanism of cationic surfactant adsorption at the solid-aqueous interface.

Until recently, the rapid time scales associated with the formation of an adsorbed surfactant layer at the solid-aqueous interface has prevented accurate investigation of adsorption kinetics. This has led to the mechanism of surfactant adsorption being inferred from thermodynamic data. These explanations have been further hampered by a poor knowledge of the equilibrium adsorbed surfactant morphology, with the structure often misinterpreted as simple monolayers or bilayers, rather than the discrete surface aggregates that are present in many surfactant-substrate systems. This review aims to link accepted equilibrium data with more recent kinetic and structural information in order to describe the adsorption process for ionic surfactants. Traditional equilibrium data, such as adsorption isotherms obtained from depletion approaches, and the most popular methods by which these data are interpreted are examined. This is followed by a description of the evidence for discrete aggregation on the substrate, and the morphology of these aggregates. Information gained using techniques such as atomic force microscopy, fluorescence quenching and neutron reflectivity is then reviewed. With this knowledge, the kinetic data obtained from relatively new techniques with high temporal resolution, such as ellipsometry and optical reflectometry, are examined. On this basis the likely mechanisms of adsorption are proposed.

Evidence of shear-dependent boundary slip in Newtonian liquids.

The flow of Newtonian fluids was studied by directly measuring the hydrodynamic drainage force acting on a sphere approaching a flat surface. Our force measurements provide clear evidence of boundary slip and show that the degree of boundary slip is a function of the liquid viscosity and the shear rate. A shear-dependent boundary slippage was also observed in experiments with a polymer (PDMS). The liquids wetted the bounding surfaces either partially or completely. Our results have important consequences for the design of microfluidic devices, and in technological processes, such as lubrication and permeability of microporous media.