Erica J. Wanless

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.

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.

Adsorbed and near-surface structure of ionic liquids determines nanoscale friction

Surface-adsorbed and near-surface ion layer structure controls nanotribology in the silica-propylammonium nitrate (PAN)-mica system. Atomic Force Microscopy (AFM) imaging and normal force curves reveal that the normal load dictates the number of interfacial ion layers and the lateral layer structure. Shear force measurements show the lubricity of the interface changes with the number, and lateral structure, of the confined ion layer(s).

Interaction forces between silica surfaces in aqueous solutions of cationic polymeric flocculants: effect of polymer charge

Three cationic polymers with molecular weights and charge density of 3.0 x 10(5) g/mol and 10% (D 6010), 1.1 x 10(5) g/mol and 40% (D6040), and 1.2 x 10(5) g/mol and 100% (D6099) were investigated in aqueous NaCl solutions in the presence of silica. The atomic force microscope (AFM) colloidal probe technique was used to determine silica interparticle interaction forces, which were compared to macroscopic information on the strength of interactions such as compressive yield stress measurements. It was found that in 30 mM NaCl solution the 10% charged polymer produced steric repulsion upon approach and long-range adhesion with multiple pull off events upon retraction at the optimum flocculation concentration. This suggests that the polymer was adsorbed in a conformation where segments extend from the surface, resulting in bridging flocculation. The 40 and 100% charged polymers produced attraction upon approach and strong adhesion with snap out from contact upon separation at optimum polymer dosages. This suggests that these polymers are adsorbed with flat conformations and is typical of charge neutralization or patch attraction. The attractions for 40 and 100% charged polymers measured with the AFM are significantly larger than for the 10% charged polymer. The polymer dose that produced the optimum flocculation and the maximum compressive yield stress typically corresponded to the polymer concentration that produced the maximum adhesion for each polymer. It was found that the magnitude of the adhesive force was more significant in determining the compressive yield stresses of the silica particle sediments than the aggregate size and structure.

Critical Salt Effects in the Swelling Behavior of a Weak Polybasic Brush

The swelling behavior of poly(2-(diethylamino)ethyl methacrylate) (PDEA) brushes in response to changes in solution pH and ionic strength has been investigated. The brushes were synthesized by ARGET ATRP methodology at the silica-aqueous solution interface via two different surface-bound initiator approaches: electrostatically adsorbed cationic macroinitiator and covalently anchored silane-based ATRP initiator moieties. The pH-response of these brushes is studied as a function of the solvated brush thickness in a constant flow regime that elucidates the intrinsic behavior of polymer brushes. In situ ellipsometry equilibrium measurements show the pH-induced brush swelling and collapse transitions are hysteretic in nature. Furthermore, high temporal resolution kinetic studies demonstrate that protonation and solvent ingress during swelling occur much faster than the brush charge neutralization and solvent expulsion during collapse. This hysteresis is attributed to the formation of a dense outer region or skin during collapse that retards solvent egress. Moreover, at a constant pH below its pKa, the PDEA brush exhibited a critical conformational change in the range 0.5-1 mM electrolyte, a range much narrower than predicted by the theory of the osmotic brush regime. This behavior is attributed to the hydrophobicity of the collapsed brush. The swelling and collapse kinetics for this salt-induced transition are nearly identical. This is in contrast to the asymmetry in the rate of the pH-induced response, suggesting an alternative mechanism for the two processes dependent on the nature of the environmental trigger.

Direct Observation of pH-Induced Coalescence of Latex-Stabilized Bubbles Using High-Speed Video Imaging

The coalescence of pairs of 2 mm air bubbles grown in a dilute electrolyte solution containing a lightly cross-linked 380 nm diameter PEGMA-stabilized poly(2-vinylpyridine) (P2VP) latex was monitored using a high-speed video camera. The air bubbles were highly stable at pH 10 when coated with this latex, although coalescence could be induced by increasing the bubble volume when in contact. Conversely, coalescence was rapid when the bubbles were equilibrated at pH 2, since the latex undergoes a latex-to-microgel transition and the swollen microgel particles are no longer adsorbed at the air-water interface. Rapid coalescence was also observed for latex-coated bubbles equilibrated at pH 10 and then abruptly adjusted to pH 2. Time-dependent postrupture oscillations in the projected surface area of coalescing P2VP-coated bubble pairs were studied using a high-speed video camera in order to reinvestigate the rapid acid-induced catastrophic foam collapse previously reported [Dupin, D.; et al. J. Mater. Chem. 2008, 18, 545]. At pH 10, the P2VP latex particles adsorbed at the surface of coalescing bubbles reduce the oscillation frequency significantly. This is attributed to a close-packed latex monolayer, which increases the bubble stiffness and hence restricts surface deformation. The swollen P2VP microgel particles that are formed in acid also affected the coalescence dynamics. It was concluded that there was a high concentration of swollen microgel at the air-water interface, which created a localized, viscous surface gel layer that inhibited at least the first period of the surface area oscillation. Close comparison between latex-coated bubbles at pH 10 and those coated with 66 microm spherical glass beads indicated that the former system exhibits more elastic behavior. This was attributed to the compressibility of the latex monolayer on the bubble surface during coalescence. A comparable elastic response was observed for similar sized titania particles, suggesting that particle size is a significant factor in defining the interfacial elasticity of particle-coated bubbles.

In situ observations of adsorbed microgel particles

The formation and morphological changes of a pH-responsive microgel layer on silica and mica were studied by tapping mode atomic force microscopy. First, lightly cross-linked, sterically-stabilised poly(2-vinylpyridine) (P2VP) particles were adsorbed in their non-solvated latex form at pH 4.8 to produce a structurally-disordered monolayer that covers the entire substrate. Addition of acid to this particulate film induces a latex-to-microgel transition at pH 3.0, causes particle swelling (and also some desorption) and produces a uniform, swollen film with localised hexagonal packing. Returning to pH 4.8 causes partial microgel deswelling to form individual oblate spheroidal P2VP latex particles, which retain the localised order previously induced by swelling. The swelling and collapse of this P2VP film was reversible during subsequent pH cycles, with no further desorption observed. The adsorbed amount of P2VP microgel/latex was quantified at each pH by determining the surface density and dimensions of the adsorbed particles. These measurements allow the microgel surface excess to be calculated for the first time. The initial adsorbed amount is less than that predicted by the standard Random Sequential Adsorption model (RSA) for hard particle adsorption, and is explained by the unexpected deformation of these high Tg particles due to their strong electrostatic attraction to the solid-liquid interface.

The roles of particles in multiphase processes: Particles on bubble surfaces

Particle-stabilised foams (or froths) form the fundamental framework of industrial processes like froth flotation. This review provides an overview of the effects of particles on bubble surfaces. The characteristics of the particles have a profound effect on the stability of the bubbles although the stabilisation mechanisms may differ. It is well known that layers of particles may provide a steric barrier between two interfaces, which prevents the coalescence of bubbles. Although perhaps considered of lesser importance, it is interesting to note that particles may affect the bubble surface and momentarily suppress coalescence despite being absent from the film separating two bubbles. Foams are at best metastable and coalescence occurs to achieve a state of minimum energy. Despite this, particles have been reported to stabilise bubbles for significant periods of time. Bubble coalescence is accompanied by a release of energy triggered by the sudden change in surface area. This produces a distinctive oscillation of the bubble surface, which may be influenced by the presence of incompressible particles yielding unique surface properties. A survey of the literature shows that the properties of these composite materials are greatly affected by the physicochemical characteristics of the particles such as hydrophobicity and size. The intense energy released during the coalescence of bubbles may be sufficient to expel particles from the bubble surface. It is noted that the detachment of particles may preferentially occur from specific locations on the bubble surface. Examination of the research accounts again reveals that the properties of the particles may affect their detachment upon the oscillation of the bubble surface. However, it is believed that most parameters affecting the detachment of particles are in fact modifying the dynamics of the three-phase line of contact. Both the oscillation of a coalescing bubble and the resulting detachment of particles are highly dynamic processes. They would greatly benefit from computer simulation studies.

Direct observation of giant pickering emulsion and colloidosome droplet interaction and stability

The interactions of two 2-mm pendant oil droplets grown in the presence of an aqueous solution of poly(glycerol monomethacrylate)-stabilized polystyrene latex particles was observed using a high-speed video camera. The coalescence behavior was monitored as a function of oil type (n-dodecane versus sunflower oil) and particle size (135 versus 902 nm), as well as in the presence and absence of an oil-soluble cross-linker [tolylene 2,4-diisocyanate-terminated poly(propylene glycol)]. The damping coefficient of the coalescing n-dodecane droplets was found to increase in the presence of the latex, demonstrating particle adsorption. Coalescence times increased when the oil phase was changed from n-dodecane to sunflower oil, because of the much higher viscosity of the latter oil. In addition, increasing the adsorbed particle size from 135 to 902 nm led to longer coalescence times because of the greater distance separating the oil droplets. Coalescence times observed in the presence of the larger 902-nm particles indicated that two different modes of contact can occur prior to a coalescence event (bilayer or bridging monolayer of particles in the film). Addition of an oil-soluble surface-active cross-linker to the sunflower oil phase to react with the hydroxy groups of the particle stabilizer reduced the interfacial elasticity and ultimately prevented coalescence after cross-linking for 20 min at 25 °C. Such giant colloidosomes can remain in contact for several hours without undergoing coalescence, which demonstrates their high stability. Furthermore, coalescence is prevented even if the cross-linker is present in only one of the pendant droplets. Finally, evidence for cross-linker diffusion from one pendant droplet to another was indicated by a visible filament connecting the two droplets upon retraction.

Adsorption of Submicrometer-Sized Cationic Sterically Stabilized Polystyrene Latex at the Air−Water Interface: Contact Angle Determination by Ellipsometry

Near-monodisperse, sterically stabilized cationic polystyrene latexes of either 122 or 310 nm diameter were prepared by aqueous emulsion polymerization using cheap, readily available reagents. At low pH, these latexes stabilized foams prepared by either hand-shaking or by using a foam column. SEM studies confirmed that the dried foam mainly comprised well-defined bilayers, which suggests that each air bubble is stabilized with a latex monolayer. Adsorption of the same latexes at the planar air-water interface was studied using the Langmuir-Blodgett trough technique. Surface pressure isotherms confirmed particle desorption from the interface on repeated compression of the latex monolayers. For the 122 nm latex at pH 2, ellipsometric analysis enabled a contact angle of approximately 43 degrees to be calculated from a simple two-layer model, which suggests that these particles have only moderate wettability. Similar results were obtained for the 310 nm latex, but the data were much less reliable in this case due to additional background particle scattering.