Interactions between nanoparticles in nanosuspension.

Nanoparticles are particles with a characteristic dimension below 100 nm. The properties of nanoparticles differ substantially from those of "big" colloidal particles (size bigger than 1 µm) because radius of surface forces, which is around 100 nm, is greater than or comparable with the nanoparticles size. The latter means that each nanoparticle could be completely covered by the surface forces of the neighbouring particles at small enough separation. It also means that the well-known Derjaguin approximation cannot be applied directly and some modifications are required. Pairwise interaction between nanoparticles can be used only at an extremely low volume fraction of nanoparticles (below some critical volume fraction, which is ~0.02%), and above this concentration a new theory based on many-particle interactions should be applied, which is yet to be developed. Some recent progress in the area of interaction between nanoparticles is reviewed and the properties of nanosuspensions based on interaction between nanoparticles are described. The authors have not attempted to cover all available literature in the area but instead have tried to underline the fundamental problems in the area which need to be addressed.

The effect of adsorption kinetics on the rate of surfactant-enhanced spreading.

A comparison of the kinetics of spreading of aqueous solutions of two different surfactants on an identical substrate and their short time adsorption kinetics at the water/air interface has shown that the surfactant which adsorbs slower provides a higher spreading rate. This observation indicates that Marangoni flow should be an important part of the spreading mechanism enabling surfactant solutions to spread much faster than pure liquids with comparable viscosities and surface tensions.

Wetting films of aqueous solutions of Silwet L-77 on a hydrophobic surface.

The formation of wetting films of aqueous solutions of Silwet L-77 on hydrophobic substrates takes place only at concentrations above the critical aggregation concentration (CAC). At concentrations above the critical wetting concentration (CWC) a new phenomenon was found: the formation of multilayered spots of thicker films in the wetting film of aqueous solutions of Silwet L-77 on hydrophobic surfaces. An expansion of the thicker spots within the film and the formation of "channels" between the spots and the edge of the film led to a continuous shrinkage of the wetting film and its disappearance in the end. We suggested that the multiple thicker films originate from the multilayer structuring of trisiloxane bilayers within the wetting film.

Surfactant-enhanced spreading: Experimental achievements and possible mechanisms.

Surfactants are broadly used to improve wetting properties of aqueous formulations. The improvement is achieved by essential reduction of liquid/air and solid/liquid interfacial tensions resulting in the decrease of contact angle. For moderately hydrophobic substrates, there is a range of surfactants providing complete wetting of substrate. With the decrease of substrate surface energy, this range of surfactants reduces very quickly and only trisiloxane surfactant solutions are capable to wet completely such highly hydrophobic substrates as polypropylene and parafilm. That is why these surfactants are referred to as superspreaders. The most intriguing feature of wetting surfactant solutions is their ability to spread much faster than pure liquids with spread area, S, being proportional to time, t, S~t, as compared to S~t(0.2) for pure liquids, which wet completely the solid substrate. Trisiloxane surfactant solutions spread faster than other aqueous surfactant solutions, which also provide complete wetting, being superspreaders in the sense of spreading rate as well. The mechanism of fast spreading of surfactant solutions on hydrophobic substrates and much higher spreading rates for trisiloxane solutions are to be explained. Below the available experimental data on superspreading and surfactant-enhanced spreading are analysed/summarised, and possible mechanisms governing the fast spreading are discussed.

Mixtures of catanionic surfactants can be superspreaders: Comparison with trisiloxane superspreader.

HYPOTHESIS: Mixed solutions of cationic and anionic surfactants show considerable synergism in their wetting behaviour, but their spreading is affected considerably by the phase separation processes. The valuable information about wetting properties of synergetic mixtures can be obtained by using mixtures in which phase separation occurs at concentrations above cmc. EXPERIMENTS: Spreading properties of mixed solutions of cationic and anionic surfactants over highly hydrophobic substrate such as polyethylene are investigated and compared with those for trisiloxane superspreader. Experiments are performed at relative humidity of 40% and 80%. Interfacial tension at water/air and water/alkane interfaces is measured to explain spreading performance. FINDINGS: Catanionic solutions can wet hydrophobic substrates nearly as effective as solutions of trisiloxane superspreader. The spreading factor reaches 70% of that of superspreader for the most effective mixed solution. The spreading slows down earlier at high surfactant concentrations. At room humidity (40%) spread area has a maximum vs concentration. However, the maximum was not observed at higher humidity 80%. Humidity does not affect the short-time spreading rate, but it influences considerably the time when spreading slows down. The spreading rate of mixed solutions is smaller than that of superspreader despite the same spreading exponent α=0.5.

Fluoro- vs hydrocarbon surfactants: why do they differ in wetting performance?

Fluorosurfactants are the most effective compounds to lower the surface tension of aqueous solutions, but their wetting properties as related to low energy hydrocarbon solids are inferior to hydrocarbon trisiloxane surfactants, although the latter demonstrate higher surface tension in aqueous solutions. To explain this inconsistency available data on the adsorption of fluorosurfactants on liquid/vapour, solid/liquid and solid/vapour interfaces are discussed in comparison to those of hydrocarbon surfactants. The low free energy of adsorption of fluorosurfactants on hydrocarbon solid/water interface should be of a substantial importance for their wetting properties.

Adsorption layer properties of alkyltrimethylammonium bromides at interfaces between water and different alkanes.

We measured the interfacial tensions of aqueous solutions against different oil phases using drop profile analysis tensiometry (PAT-1, Sinterface Technologies, Germany) for decyl- and dodecyltrimethylammonium bromide (C10TAB and C12TAB) in phosphate buffer (10 mM, pH7). The following alkanes were used as oil phases: hexane, heptane, octane, nonane, decane, dodecane and tetradecane. The obtained equilibrium interfacial tension isotherms were fitted by the Frumkin Ionic Compressibility model (FIC). The surfactants adsorb at the water/oil interface in competition with the oil molecules. At high surfactant surface coverage this competitive adsorption is manifested in two ways. First, for short chain surfactants, the oil molecules are embedded into the adsorption layer. Second, for long chain surfactants, the short alkane chains of the oil molecules are squeezed out from the adsorption layer due to strong mutual interaction between surfactants' chains.

Effect of water hardness on surface tension and dilational visco-elasticity of sodium dodecyl sulphate solutions.

The complementary drop and bubble profile analysis and maximum bubble pressure tensiometry are used to measure the dynamic surface tension of aqueous SDS solutions in the presence of hardness salts (CaCl(2) and MgCl(2) in the ratio of 2:1 at concentrations of 6 and 40FH). The presence of hardness salts results in an essential increase of the SDS adsorption activity, which indicates the formation of Ca(DS)(2) and Mg(DS)(2) in the SDS solutions. The surface tension isotherms of SDS in presence of Ca(DS)(2) and Mg(DS)(2) are described using the generalised Frumkin model. The presence of hardness salts accelerates the ageing of SDS solutions as compared with the addition of 0.01 M NaCl due to a faster hydrolysis and hence formation of dodecanol. These results are used to estimate the possible concentration of dodecanol in the studied SDS solutions. The buoyant bubble profile method with harmonic surface oscillations is used to measure the dilational rheology of SDS solutions in presence of hardness salts in the frequency range between 0.005 Hz and 0.2 Hz. The visco-elasticity modulus in the presence of hardness salts is higher as compared with its values in the presence of 0.01 M NaCl additions. The ageing of SDS solutions leads to an essential increase of the visco-elastic modulus.

Ionic strength and pH as control parameters for spontaneous surface oscillations.

A system far from equilibrium, where the surfactant transfer from a small drop located in the aqueous bulk to the air-water interface results in spontaneous nonlinear oscillations of surface tension, is theoretically and experimentally considered. The oscillations in this system are the result of periodically arising and terminating Marangoni instability. The surfactant under consideration is octanoic acid, the dissociated form of which is much less surface-active than the protonated form. Numerical simulations show how the system behavior can be controlled by changes in pH and ionic strength of the aqueous phase. The results of numerical simulations are in good agreement with experimental data.

Aggregation in colloidal suspensions: effect of colloidal forces and hydrodynamic interactions.

The forces acting in colloidal suspensions and affecting their stability and aggregation kinetics are considered. The approximations used for these forces in numerical simulations and the importance of the balanced account for both colloidal forces and hydrodynamic interactions are discussed. As an example the results of direct numerical simulations of kinetics of aggregation either with account for hydrodynamic interaction between particles or without it are compared by varying the parameters of the interaction potential between particles and fraction of solid. Simulations are based on the Langevin equations with pairwise interaction between particles and take into account Brownian, hydrodynamic and colloidal forces. It is confirmed that the neglecting of hydrodynamic interaction results in an accelerated growth of aggregates. The results of numerical simulations of aggregation kinetics are compared with well known analytical solutions.

Dynamics of interfacial layers-experimental feasibilities of adsorption kinetics and dilational rheology.

Each experimental method has a certain range of application, and so do the instruments for measuring dynamic interfacial tension and dilational rheology. While the capillary pressure tensiometry provides data for the shortest adsorption times starting from milliseconds at liquid/gas and tens of milliseconds at liquid/liquid interfaces, the drop profile tensiometry allows measurements in a time window from seconds to many hours. Although both methods together cover a time range of about eight orders of magnitude (10(-3) s to 10(5) s), not all surfactants can be investigated with these techniques in the required concentration range. The same is true for studies of the dilational rheology. While drop profile tensiometry allows oscillations between 10(-3) Hz and 0.2 Hz, which can be complemented by measurements with capillary pressure oscillating drops and the capillary wave damping method (up to 10(3) Hz) these six orders of magnitude in frequency are often insufficient for a complete characterization of interfacial dilational relaxations of surfactant adsorption layers. The presented analysis provides a guide to select the most suitable experimental method for a given surfactant to be studied. The analysis is based on a diffusion controlled adsorption kinetics and a Langmuir adsorption model.

Auto-oscillation of surface tension: effect of pH on fatty acid systems.

Spontaneous nonlinear oscillations of surface tension produced by transfer of either octanoic or nonanoic acids from a droplet situated in the bulk water to the air/water interface are studied experimentally. It is shown that the oscillation amplitude decreases significantly with the increase of pH of aqueous phase. At pH > 6.5, detectable oscillations for the two fatty acids studied do not exist. The results are discussed in terms of the mechanism proposed recently for spontaneous oscillations produced by transfer of nonionic surfactants.

Recognition and dissociation kinetics in the interfacial molecular recognition of barbituric acid by amphiphilic melamine-type monolayers.

Progress in the understanding of interfacial molecular recognition kinetics is obtained by use of the sweeping technique for experimental studies of the reaction kinetics between a host monolayer and a non-surface-active species dissolved in the aqueous subphase. The experimental results show that the interfacial recognition reaction between a 2C(11)H(23)-melamine (2,4-di(n-undecylamino)-6-amino-1,3,5-triazine) monolayer and dissolved barbituric acid is reversible when the 2C(11)H(23)-melamine/barbituric acid monolayer is transferred back onto a pure water subphase. The kinetics of the recognition and dissociation reaction is experimentally and theoretically investigated. The approximate additive theoretical model developed recently is extended to consider the dissociation kinetics of the interfacial supramolecular complex. The kinetic constants for the recognition and dissociation reactions in the mixed monolayer consisting of 2C(11)H(23)-melamine and 2C(11)H(23)-melamine/barbituric acid complex are determined. It is shown that the kinetic constant of the recognition reaction is nearly independent of temperature, whereas that of the dissociation reaction increases with increasing temperature.

Surfactant transfer through a liquid membrane: origin of spontaneous oscillations at the membrane/acceptor phase interface.

Instability due to surfactant redistribution in a liquid membrane system consisting of two solutions, namely source and acceptor, separated by a layer of immiscible liquid is studied theoretically and experimentally. The transfer of a surfactant from a source phase to an acceptor phase is often accompanied by spontaneous nonlinear oscillations of electrical potential and/or interfacial tension. The oscillations can be generated at each of the membrane interfaces. Here a mechanism of oscillation, which develops at the membrane/acceptor phase interface, is proposed on the basis of direct numerical simulation of the system evolution. Performed experimental studies confirm the theoretical results.

Marangoni instability and spontaneous non-linear oscillations produced at liquid interfaces by surfactant transfer.

The systems producing non-linear spontaneous oscillations of the interfacial tension and electric potential are considered and the available criteria for development of convective instability by the surfactant transfer through a liquid interface are discussed. The non-linear oscillations are observed by the surfactant transfer from a point-like source situated in the bulk of liquid, by the transfer of two ionic solutes through a liquid interface in two opposite directions, and by the transfer of ionic solutes through a liquid membrane. All these systems are governed by more complicated mechanisms than merely arising oscillatory convective instability. The main experimental results obtained for these three systems as well as theoretical models proposed for their explanation are discussed.

Effect of buoyancy on appearance and characteristics of surface tension repeated auto-oscillations.

The effect of buoyancy on spontaneous repeated nonlinear oscillations of surface tension, which appear at the free liquid interface by dissolution of a surfactant droplet under the interface, is considered on the basis of direct numerical simulation of the model system behavior. The oscillations are the result of periodically rising and fading Marangoni instability. The buoyancy force per se cannot lead to the oscillatory behavior in the considered system, but it influences strongly both the onset and decay of the instability and therefore, affects appearance and characteristics of the oscillations. If the surfactant solution density is smaller than the density of the pure liquid, then the buoyancy force leads to a considerable decrease of the induction period and the period of oscillations. The buoyancy force affects also the dependence of the oscillation characteristics on the system dimensions. The results of the simulations are compared with the available experimental data.

Nonlinear spontaneous oscillations at the liquid/liquid interface produced by surfactant dissolution in the bulk phase.

The results of theoretical and experimental studies of spontaneous nonlinear oscillations produced at the liquid/liquid interface by surfactant transfer from a point source situated in one of the bulk phases are presented. The theoretical analysis is based on the direct numerical simulation of the system evolution. The experiments are performed for the heptane/water interface using middle-chain aliphatic alcohols as surfactants. The results for the oil/water interface are compared with the corresponding data obtained for the air/water interface. The presented results allow the conclusion that auto-oscillations at the air/liquid and liquid/liquid interfaces are governed by very similar mechanisms but their characteristics are strongly dependent on the properties of the two contacting media, in particular, on the surfactant partition coefficient.

Effect of substance properties on the appearance and characteristics of repeated surface tension auto-oscillation driven by Marangoni force.

The effect of substance properties (solution viscosity and density, surfactant bulk and surface diffusion coefficient, activity, and solubility) on the appearance and characteristics of surface tension auto-oscillation that occurs by dissolution of a surfactant drop under the water-air interface is considered in the framework of a simple mathematical model, taking into account the convection driven by the Marangoni effect and convective diffusion together with adsorption/desorption processes at the air-water interface. Numerical simulations show that apart from the Marangoni and Schmidt number, the system behavior is governed also by the exchange number, which determines the surfactant exchange with the interface. The criterion for the instability onset in a system with both normal and tangential (with respect to the interface) concentration gradient, the correlation between the global and local Marangoni numbers, as well as a comparison with experiment are discussed.

Experimental studies on the geometrical characteristics determining the system behavior of surface tension autooscillations.

Autooscillation of the surface tension is a phenomenon related to Marangoni instability periodically arising and fading by dissolution of a surfactant droplet under a water-air interface. A detailed experimental investigation was performed to clear up the influence of the system geometry on development and characteristics of autooscillations. It was found that the aspect ratio is an additional dimensionless parameter that determines the system behavior equally to the Marangoni number. The influence of the cell diameter, capillary immersion depth, and droplet radius on the autooscillation period and amplitude was studied as well.

Theoretical description of repeated surface-tension auto-oscillations.

A mathematical model is proposed to follow the behavior of a system where a droplet of a surfactant with limited solubility on the tip of a capillary under the free liquid surface dissolves in a container with a unity aspect ratio. Numerical simulations show that instability repeatedly arises and fades in the system, resulting in auto-oscillations of the surface tension in agreement with the experimental data. The system evolution during the oscillation is discussed in detail. It is established that the presence of a boundary in the radial direction is a necessary precondition for the appearance of the second and following oscillations.