Soft matter dynamics: A versatile microgravity platform to study dynamics in soft matter.

We describe an experiment container with light scattering and imaging diagnostics for experiments on soft matter aboard the International Space Station (ISS). The suite of measurement capabilities can be used to study different materials in exchangeable sample cell units. The currently available sample cell units and future possibilities for foams, granular media, and emulsions are presented in addition to an overview of the design and the diagnostics of the experiment container. First results from measurements performed on ground and during the commissioning aboard the ISS highlight the capabilities of the experiment container to study the different materials.

New view of the adsorption of surfactants at water/alkane interfaces - Competitive and cooperative effects of surfactant and alkane molecules.

The theoretical description of the adsorption of surfactants at interfaces between aqueous solutions and oil was based over a very long time on models derived for the solution/air interface. Thus, most of the experimentally observed peculiarities could not be specifically considered but were merely interpreted in terms of a penetration of oil molecules into the alkyl chain layer of the adsorbed surfactant molecules. These penetrating oil molecules enhance the surfactant adsorption as compared to the water/air interface. Later on, for the special situations at water/oil interfaces a competitive adsorption of surfactant and oil molecules was postulated, allowing a much better description of experimental data. This picture, however, was unable to explain why the interfacial tension of the water/oil interface decreases very quickly when extremely small amounts of surfactants are added to the water. This effect cannot be of competitive nature, but a cooperativity of surfactant and oil molecules forming a mixed adsorption layer is required instead. This cooperative effect means that already few surfactant molecules adsorbed at the interface can induce a significant ordering of oil molecules in the interfacial layer. This new interfacial structure, in turn, attracts further surfactant molecules to adsorb. Improving the theoretical description of experimental data was finally achieved by applying suitable adsorption models for the two adsorbing compounds, i.e. a Frumkin adsorption model for the oil molecules and a Langmuir, Frumkin, or reorientation model for the adsorbing surfactant molecules. Here, the progress in modelling surfactant adsorption at water/oil interfaces is discussed mainly for the homologous series of the cationic surfactants CnTAB, of the anionic surfactant SDS, and members of the homologous series of the non-ionic surfactants CnDMPO at water/alkane interfaces.

Surface dilational rheological properties in the nonlinear domain.

The interfacial tension response to dilational deformation of interfacial area exhibits a (more or less) nonlinear behavior, depending on the amplitude of the deformation. Studies of such observable interfacial properties in the nonlinear domain suggest valuable information about the two-dimensional microstructure of the interfacial layer, as well as about the structure time-evolution. In this article, the emphasis is centered on the available mathematical methods for quantitatively analyzing and describing the magnitude and the characteristics of the nonlinear interfacial viscoelastic properties. Specifically, in periodic oscillation experiments the nonlinear behavior can be represented by the combination of a linear part (the surface dilational modulus), with an additional complementary Fourier analysis parameterizing the nonlinearity. Also asymmetric Lissajous plots, of interfacial tension versus deformation, are useful tools for expanding the response nonlinearity into four distinct components relevant to significant points of the cyclic loop. In connection with the mathematical methods, nonequilibrium thermodynamic formulations provide a powerful theoretical framework for investigating the interfacial dynamic properties of multiphase systems. Experimental results for adsorption layers of complex components, available in the literature, show notable nonlinear interfacial viscoelastic behavior. In particular in this review, data are illustrated for solutions of polymers and of polyelectrolyte/surfactant complexes. The observed nonlinear findings reveal formation of complexes, patches, and other different interfacial structures.

Smart and green interfaces: from single bubbles/drops to industrial environmental and biomedical applications.

Interfaces can be called Smart and Green (S&G) when tailored such that the required technologies can be implemented with high efficiency, adaptability and selectivity. At the same time they also have to be eco-friendly, i.e. products must be biodegradable, reusable or simply more durable. Bubble and drop interfaces are in many of these smart technologies the fundamental entities and help develop smart products of the everyday life. Significant improvements of these processes and products can be achieved by implementing and manipulating specific properties of these interfaces in a simple and smart way, in order to accomplish specific tasks. The severe environmental issues require in addition attributing eco-friendly features to these interfaces, by incorporating innovative, or, sometimes, recycle materials and conceiving new production processes which minimize the use of natural resources and energy. Such concept can be extended to include important societal challenges related to support a sustainable development and a healthy population. The achievement of such ambitious targets requires the technology research to be supported by a robust development of theoretical and experimental tools, needed to understand in more details the behavior of complex interfaces. A wide but not exhaustive review of recent work concerned with green and smart interfaces is presented, addressing different scientific and technological fields. The presented approaches reveal a huge potential in relation to various technological fields, such as nanotechnologies, biotechnologies, medical diagnostics, and new or improved materials.

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.

From spherical to polymorphous dispersed phase transition in water/oil emulsions.

Optical scanning tomography is used to characterize bulk properties of transparent water-in-paraffin oil emulsions stabilized with hexadecyl-trimethylammonium bromide (CTAB) and silica nanoparticles. A flow of 500 hundred images is used to analyze each scanning shot with a precision of about 1 microm. The role of silica particles in the shape of the water droplets is investigated. Depending on the concentration of CTAB and silica nanoparticles, a transition occurs in their geometry that changes from spherical to polymorphous. This transition is controlled by the ratio R=[CTAB]/[SiO2] and is described using an identification procedure of the topology of the gray level contours of the tomographic images. The transition occurs for Rcrit approximately 3x10(-2) and is shown to correspond to a pH of the dispersed phase of 8.5.

Rheological surface properties of C12DMPO solution as obtained from amplitude- and phase-frequency characteristics of an oscillating bubble system.

The experimental data on the surface rheological characteristics of dodecyl dimethyl phosphine oxide solutions obtained in a fully automatic oscillating bubble device under microgravity conditions in the frequency range 0.01-100 Hz are presented. The complex surface elasticity modulus is obtained form the amplitude- and phase-frequency characteristics of established pressure oscillations in a closed cell without calibration experiments by direct calculation of the necessary coefficients. The characteristics of the adsorption layers obtained from the elasticity modulus are in good agreement with adsorption isotherms and equations of state accounting for the intrinsic (2D) monolayer compressibility.

Adsorption and surface rheology of n-dodecanol at the water/air interface.

Adsorption layers of n-dodecanol at the water/air interface show phase transitions at low temperatures [Vollhardt, Fainerman, Emrich, J. Phys. Chem. B 104 (2000) 8536]. Using a drop shape technique it is shown that the dilational elasticity disappears in the coexistence region of the adsorption layer. The relaxation time between the condensed and liquid-like surface states is in the sub-second time range.

Frequency characteristics of amplitude and phase of oscillating bubble systems in a closed measuring cell.

The amplitude- and phase-frequency characteristics of oscillating bubble systems with a closed measuring cell are analyzed. The shape of the frequency characteristics is qualitatively different for bubbles smaller or larger than a hemisphere, respectively, and also for diluted and concentrated surfactant solutions. Moreover, the presence of a surfactant in the solution strongly influences the characteristic frequencies of the system. The experiments performed under ground and microgravity conditions show a good qualitative agreement with theoretically predicted amplitude- and phase-frequency characteristics and confirm the adequacy of the proposed theory. The comparison of high-frequency limits of the surface dilatational elasticity with the theoretical Gibbs elasticities calculated according to the respective adsorption isotherm shows good agreement for small surfactant concentrations. At higher concentrations large discrepancies are observed which can possibly be explained by the violation of the linearity condition for the surface layer.

Effect of surfactant interfacial orientation/aggregation on adsorption dynamics.

The application of new thermodynamic adsorption isotherms allow to improve the description of surfactant adsorption kinetics based on a diffusional transport. While the consideration of interfacial reorientation corrects apparently too high diffusion coefficients, interfacial aggregation avoids too small diffusion coefficients or the assumption of adsorption barriers. The adsorption kinetics of alkyl dimethyl phosphine oxides is influenced by interfacial reorientation. While the lower homologues (C8-C12) follow the classical diffusion model, the higher homologues (C13-C15) yield diffusion coefficients several times larger than the physically reasonable values. Assuming two different adsorption states, the resulting diffusion coefficients agree with those expected from the geometric size of the molecules. The model also works well for oxyethylated non-ionics, such as C10EO8. As a second example, a good theoretical description is obtained for experiments of 1-decanol solutions when a mean surface aggregation number of n = 2.5 is assumed. The same n was obtained from the description of the equilibrium adsorption isotherm of 1-decanol. Assuming that the transition from one into the other state is controlled by a rate constant (change in orientation, formation or disintegration of two-dimensional aggregates) significant changes in the kinetics curves can result. The use of additional rate constants yields an improved fitting to experimental data.

Adsorption and partitioning of surfactants in liquid-liquid systems.

The adsorption at liquid-liquid interfaces is a phenomenon with a remarkable impact on many scientific and technological fields concerning multiphasic systems. Though in principle similar to liquid-vapour, the study and the description of the dynamic aspects of the adsorption processes at liquid-liquid interfaces deserves some specific considerations. In fact, these systems are often characterised by the partitioning of the surfactant between the two liquid phases, which makes much more complex both their modelling and investigation. In some conditions, the partitioning can be the main process controlling the adsorption dynamics. This paper is aimed at reviewing the state-of-the-art of the theoretical modelling and experimental investigation of the adsorption dynamics of surfactants at liquid-liquid interfaces. After a brief introduction to the problem of adsorption dynamics, the principal models utilised to describe the process at liquid-liquid interfaces under different assumptions are critically presented, underlining the influence of the surfactant partitioning, with respect to the relative volumes of the liquid phases and of the initial partitioning conditions. The most important experimental methodologies for the measurement of the dynamic interfacial tension are also critically reviewed by pointing out the specific problems related with the investigation of the adsorption dynamics of surfactants at liquid-liquid interfaces. Moreover, the problem of the measurement of the thermodynamic quantities characterising the partitioning--mainly the partition coefficient--is also addressed, reporting some literature data. Finally, a review of the literature about the experimental work on the subject and an overview of the needs and of the open questions is given.

Adsorption Kinetics of Alkylphosphine Oxides at Water/Hexane Interface

A pendant drop technique has been used to study the adsorption of a nonionic surfactant, an alkyldimethylphosphine oxide (C13DMPO), at the water/hexane interface. The measured interfacial tensions exhibit a steep initial decrease, pass through a minimum, and then level off at a value which depends on the initial surfactant concentration in the drop. This time dependence of the interfacial tension can be interpreted by an adsorption with a subsequent transfer of the surfactant into the second bulk phase, hexane. Measurements of the distribution coefficient show that the solubility of C13DMPO is much higher in hexane than in water. A qualitative model is proposed which describes the observed dynamic interfacial tensions.

Adsorption Kinetics of Alkylphosphine Oxides at Water/Hexane Interface

A theoretical model is presented to describe the adsorption of surfactant molecules at the water/oil interface for the case when transport across the interface must be considered due to the solubility of the surfactant in both liquid phases (aqueous solution drop in an oil phase). The theory is based on a diffusion-controlled adsorption model and a numerical difference scheme is used to solve the problem for closed finite systems. By simulating adsorption-desorption processes, the influence of the geometrical and thermodynamic parameters on the dynamic adsorption behavior is studied. In particular, the effects of the volume ratio, surfactant concentration, diffusion coefficients, and distribution coefficient on the process are analyzed. The model allows quantitative interpretation of the experimental data obtained for an alkyldimethylphosphine oxide at the water/hexane interface. The interfacial tension signals, presenting a minimum under some conditions, are fitted by the theoretical curves.