A. Javadi

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.

Adsorption of β-casein-surfactant mixed layers at the air-water interface evaluated by interfacial rheology.

This work presents a detailed study of the dilational viscoelastic moduli of the adsorption layers of the milk protein β-casein (BCS) and a surfactant at the liquid/air interface, over a broad frequency range. Two complementary techniques have been used: a drop profile tensiometry technique and an excited capillary wave method, ECW. Two different surfactants were studied: the nonionic dodecyldimethylphosphine oxide (C12DMPO) and the cationic dodecyltrimethylammonium bromide (DoTAB). The interfacial dilational elasticity and viscosity are very sensitive to the composition of protein-surfactant mixed adsorption layers at the air/water interface. Two different dynamic processes have been observed for the two systems studied, whose characteristic frequencies are close to 0.01 and 100 Hz. In both systems, the surface elasticity was found to show a maximum when plotted versus the surfactant concentration. However, at frequencies above 50 Hz the surface elasticity of BCS + C12DMPO is higher than the one of the aqueous BCS solution over most of the surfactant concentration range, whereas for the BCS + DoTAB it is smaller for high surfactant concentrations and higher at low concentrations. The BCS-surfactant interaction modifies the BCS random coil structure via electrostatic and/or hydrophobic interactions, leading to a competitive adsorption of the BCS-surfactant complexes with the free, unbound surfactant molecules. Increasing the surfactant concentration decreases the adsorbed proteins. However, the BCS molecules are rather strongly bound to the interface due to their large adsorption energy. The results have been fitted to the model proposed by C. Kotsmar et al. ( J. Phys. Chem. B 2009 , 113 , 103 ). Even though the model describes well the concentration dependence of the limiting elasticity, it does not properly describe its frequency dependence.

Thermodynamics of adsorption of ionic surfactants at water/alkane interfaces

On the basis of experimental data for the homologous series of alkyltrimethylammonium bromides (CnTAB) the equilibrium surface tension isotherms at three types of liquid-fluid interfaces are discussed: solution/air, solution/alkane vapor and solution/liquid alkane interfaces. It is shown that the adsorption characteristics can be described at all three interfaces by the same thermodynamic approach. In the presence of alkane molecules (in the liquid alkane phase or in the alkane vapor phase) the CnTAB adsorption layers can be best described by a co-adsorption of the alkane molecules.

Capillary pressure studies under low gravity conditions.

For the understanding of short-time adsorption phenomena and high-frequency relaxations at liquid interfaces particular experimental techniques are needed. The most suitable method for respective studies is the capillary pressure tensiometry. However, under gravity conditions there are rather strong limitations, in particular due to convections and interfacial deformations. This manuscript provides an overview of the state of the art of experimental tools developed for short-time and high-frequency investigations of liquid drops and bubbles under microgravity. Besides the brief description of instruments, the underlying theoretical basis will be presented and limits of the applied methods under ground and microgravity conditions will be discussed. The results on the role of surfactants under highly dynamic conditions will be demonstrated by some selected examples studied in two space shuttle missions on Discovery in 1998 and Columbia in 2003.

Dynamics of drops – Formation, growth, oscillation, detachment, and coalescence.

Single drops or bubbles are frequently used for the characterization of liquid-fluid interfaces. Their advantage is the small volume and the various protocols of their formation. Thus, several important methods are based on single drops and bubbles, such as capillary pressure and profile analysis tensiometry. However, these methods are often applied under dynamic conditions, although their principles are defined under equilibrium conditions. Thus, specific attention has to be paid when these methods are used beyond certain limits. In many cases, computational fluid dynamics (CFD) simulations have allowed researchers, to extend these limits and to gain important information on the interfacial dynamics. Examples discussed here are the capillary pressure tensiometry used for short time and profile analysis tensiometry for long time dynamic interfacial tension measurements, the oscillating drop methods for measuring dilational visco-elasticity. For measuring the coalescence of two drops the liquid dynamics of the subsequently formed liquid bridges have to be considered. In this paper, a thorough review of important experimental and computational findings, related to the dynamics of drops, including its formation, growth, oscillation, detachment, and coalescence is presented. Emphasis is however on some selected important developments. In addition, the paper tries to predict the main directions of advancement in interfacial research for the near future.

Oscillatory Transient Flow Experiments and Analysis in Circular Microchannels

In this research purely oscillation fluid flow in two microtubes 150 and 250 μm (3.5 mm length) is studied using computational fluid dynamic (CFD) approach and utilizing a new experimental setup developed for dynamic interfacial tension measurement (capillary pressure technique) in the frequency range between 0.2 and 80 Hz. The experiments are done with pure water at a mean temperature of about 25 °C. The results of oscillatory conditions for microtubes of 0.5 mm in diameter have been compared with experimental results for several frequencies. The computational approach was validated by comparison with experimental data of the continuous constant flow through microtubes and also with experimental results of an oscillatory flow through the same tubes at up to 25 Hz. For evaluation of the effects of hydrodynamic relaxation time th = R2 / ν on the amplitude of the pressure gradient, CFD simulation of the oscillatory flow through microtubes of 0.3 and 0.5 mm (diameter) with th =0.0225 s and 0.0625 s have been provided to compare with own corresponding maximum continuous flow (CMCF) experimental data for each frequency which occurs at maximum speed of sinusoidal motion of the piezo. The comparison demonstrates that for a microtube of 0.5 mm and th =0.0625 s for frequencies F〈(1/th ) ≤ 16 Hz the computational results for amplitude of pressure gradient is in relatively good agreement with own CMCF experimental data, while for microtubes of 0.3 mm in diameter this agreement is observed for frequencies lower than F〈(1/th ) ≤ 44 Hz. CFD simulations of the velocity profile of oscillatory flow through these microtube support these findings and show a parabolic velocity profile (like Poiseuille flow) for frequencies ≤ 10 Hz for microtube of 0.5 mm diameter while this situation is observed below 40 Hz for microtubes of 0.3 mm diameter. Although for a smaller microtube size a relatively developed flow occurs in a higher frequency range, turbulence effects can appear sooner due to the higher flow rates and consequently higher Reynolds numbers. The combination of these two opposite effects would have to be considered when comparing the flow field through microtubes of different size.Copyright

Characterisation of alkyl amines at the water/air surface with the drop and bubble profile analysis tensiometry

Pendant drop and buoyant bubble methods have been used to study the surface characteristics of alkyl amines at the water/air surface. The investigated alkyl amines, triethylamine and octylamine, showed unusual changes in the surface tension as a function of time: an initially steep drop and a subsequent steady increase in the surface tension until a value close to the one of the pure water/air system was observed. This phenomenon is explained by the evaporation of the alkyl amines, for which several sets of experiments have been conducted with the pendant drop and buoyant bubble methods. Using an appropriate experimental protocol, the equilibrium adsorption behaviour of the two amines can be quantitatively measured.

The Role of Electrostatic Repulsion on Increasing Surface Activity of Anionic Surfactants in the Presence of Hydrophilic Silica Nanoparticles

Hydrophilic silica nanoparticles alone are not surface active. They, however, develop a strong electrostatic interaction with ionic surfactants and consequently affect their surface behavior. We report the interfacial behavior of n-heptane/anionic-surfactant-solutions in the presence of hydrophilic silica nanoparticles. The surfactants are sodium dodecyl sulfate (SDS) and dodecyl benzene sulfonic acid (DBSA), and the diameters of the used particles are 9 and 30 nm. Using experimental tensiometry, we show that nanoparticles retain their non-surface-active nature in the presence of surfactants and the surface activity of surfactant directly increases with the concentration of nanoparticles. This fact was attributed to the electrostatic repulsive interaction between the negatively charged nanoparticles and the anionic surfactant molecules. The role of electrostatic repulsion on increasing surface activity of the surfactant has been discussed. Further investigations have been performed for screening the double layer charge of the nanoparticles in the presence of salt. Moreover, the hydrolysis of SDS molecules in the presence of silica nanoparticles and the interaction of nanoparticles with SDS inherent impurities have been studied. According to our experimental observations, silica nanoparticles alleviate the effects of dodecanol, formed by SDS hydrolysis, on the interfacial properties of SDS solution.

Thermodynamic Models for the Adsorption of Alkyl Trimethyl Ammonium Bromides at the Water/Hexane Interface

Based on surface/interfacial tension isotherms measured for the homologous series of alkyl trimethyl ammonium bromides (CnTAB) using the drop profile analysis tensiometry the adsorption behavior at three different liquid-fluid interfaces is discussed: solution/air, solution/hexane vapor and solution/hexane bulk liquid. The adsorption behavior can be described by different models. In the presence of hexane molecules (as a bulk liquid or as vapor in the air phase) the adsorption of the CnTAB molecules can be best described by a competitive adsorption with hexane molecules. This competitive thermodynamic model can be applied successfully to all three interfaces.

Adsorption of equimolar aqueous sodium dodecyl sulphate/dodecyl trimethylammonium bromide mixtures at solution/air and solution/oil interfaces

Two oppositely charged surfactants in an aqueous solution interact with each other via electrostatic interactions and produce surfactant complexes—catanionics. However, their quantitative influence on the interfacial tension at the solution/air and solution/oil interfaces is still unknown. We have measured the interfacial tension of sodium dodecyl sulphate (SDS) and dodecyltrimethylammonium bromide (DoTAB) aqueous mixtures using the du Nouy ring tensiometer and drop profile analysis tensiometry (PAT-1). For the oil phase, we used hexane. The obtained kinetic and equilibrium experimental results were fitted with the common theoretical Frumkin adsorption model. We found that SDS + DoTAB complexes show much higher surface activity than the single surfactants. At solution/air and solution/oil interfaces, SDS and DoTAB produce ion pairs with low water affinity and relatively low oil solubility. SDS + DoTAB partition coefficient between hexane and water phases is 0.32. Such surfactant complexes with advanced surface characteristics may be beneficial in different industrial branches nowadays.