P. Pandolfini

Drop and bubble shape analysis as tool for dilational rheology studies of interfacial layers.

Drop and bubble shape tensiometry is a modern and very effective tool for measuring dynamic and static interfacial tensions. An automatic instrument with an accurate computer controlled dosing system is discussed in detail. Due to an active control loop experiments under various conditions can be performed: constant drop/bubble volume, surface area, or height, trapezoidal, ramp type, step type and sinusoidal area changes. The theoretical basis of the method, the fitting procedure to the Gauss-Laplace equation and the key procedures for calibration of the instrument are analysed and described.

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.

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.

Oscillation of interfacial properties in liquid systems: assessment of harmonic distortion

The total harmonic distortion (THD) parameter is applied to oscillation experiments involving interfacial phases. The THD-value appears a suitable index which can be used for a quantitative estimation of the goodness of the linearity hypothesis, as assumed in the theoretical interpretation of the interfacial excitation-response behaviour. Example experimental results grant a validity domain of the linearity hypothesis and an amplitude-range tolerability for the external forcing excitation.

Calibration parameters of the pendant drop tensiometer: assessment of accuracy

A method is reported for verifying and controlling the accuracy of the calibration parameters, operating in image acquisition, for drop and bubble shape-analysis tensiometry. An error, impartially affecting the calibration parameters of both Cartesian axes, results in a squared error for the determined surface tension. Moreover, in the case where the calibration factors are affected by different errors, the determined value of surface tension is definitely unreliable, depending on the drop (or bubble) size and showing spurious in-phase or out-of-phase alterations. A procedure is illustrated for correcting the calibration parameters, on the basis of the observed results for a reference liquid. Method and procedure are validated by numerical examples.

Optical Observation of High-Frequency Drop Oscillations by a Spectrum Compression Technique applied to the Capillary Pressure Tensiometry

Image acquisition and subsampling of periodic high-frequency drop oscillations is presented as an advantageous metrological procedure in capillary pressure tensiometry (CPT). The observation of a finite sequence of single tone or of multiharmonic cycles, subsampled in an expanded time-scale interval, allows the characteristics of the real oscillations to be well-reconstructed in a frequency-compressed spectrum, where each component is translated toward lower frequencies. The introduced technique is applied to nanoliter-sized water drops, oscillating in a hydrocarbon matrix up to 150 Hz frequency, by using a standard PAL CCD camera provided with an electronic shutter. Application examples show the important role of this technique in data analysis and interpretation of typical high-frequency oscillating drop/bubble experiments. In particular, this technique is effective to check the onset of critical hydrodynamic effects and allows for the determination of the intrinsic elasticity of the liquid/cell system as a function of frequency by comparison of the liquid volume, as displaced by a piezo-actuator, and the actually observed drop volume-amplitude oscillation. The knowledge of this quantity is fundamental for the calculation of the dilational viscoelasticity from the acquired pressure data in the CPT.

Dynamic interfacial tensions in the short time range by applying a fast capillary pressure technique

The capillary pressure technique is the method of choice for any tensiometry measurements in microgravity, as all bubbles and drops have a spherical shape. A combination of fast drop formation based on a known constant liquid flow and fast data acquisition of measured capillary pressure gives access to dynamic interfacial tensions in the range of milliseconds. Also the maximum drop pressure method, an equivalent to the maximum bubble pressure technique as fastest dynamic surface tension method, can be practised by the same set-up. The technique was developed already 15 years ago [ii] and now further refined during the MAP FASES* supported by the European Space Agency [ii]. Besides a detailed description of the technical parameters, experimental results for emulsion relevant systems are presented. The set-up presented here is based on a commercial drop and bubble profile analysis tensiometer which appears to be a kind of in-situ technique for membrane emulsification processes. The instrumental set-up is suitable also for oscillating drop and bubble experiments up to frequencies of several hundreds Hz.The capillary pressure technique is the method of choice for any tensiometry measurements in microgravity, as all bubbles and drops have a spherical shape. A combination of fast drop formation based on a known constant liquid flow and fast data acquisition of measured capillary pressure gives access to dynamic interfacial tensions in the range of milliseconds. Also the maximum drop pressure method, an equivalent to the maximum bubble pressure technique as fastest dynamic surface tension method, can be practised by the same set-up. The technique was developed already 15 years ago [ii] and now further refined during the MAP FASES* supported by the European Space Agency [ii]. Besides a detailed description of the technical parameters, experimental results for emulsion relevant systems are presented. The set-up presented here is based on a commercial drop and bubble profile analysis tensiometer which appears to be a kind of in-situ technique for membrane emulsification processes. The instrumental set-up is suitable also for oscillating drop and bubble experiments up to frequencies of several hundreds Hz.

STS-107 OV-102 mission FAST experiment: Slow surface relaxation at the solution-air interface

The experiments are aimed at the study of the interfacial dilational properties, under microgravity conditions. The examined systems are aqueous solutions of the surfactant n-dodecyl-dimethylphosphine oxide, at different concentrations and temperatures. Low frequency harmonic disturbances are imposed to the interfacial area of an air bubble. Also square pulse disturbances are imposed to each studied system. The experimental results grant information about the dynamics of air-liquid single interfaces.

Rheological studies with spherically shaped thin liquid films

The present work shows the first experimental and theoretical results for investigations on the rheology of liquid films. The experiments are planned to be performed under microgravity conditions. This environment will allow forming films of different thickness, which is impossible under ground conditions due to drainage. Then the films are forced to harmonic oscillations of the film area so that the film elasticity can be measured as a function of frequency. The presented theoretical model demonstrates the main relationships to be solved under corresponding boundary conditions

Oscillating bubble tensiometer: application for studying the interfacial properties of clouds and aerosols.

Abstract We illustrate functionality and performances of the oscillating bubble tensiometer, used for studying the influence of atmospheric organic carbon on the interfacial properties of clouds and aerosols. We report experimental observations of the responses of dynamic surface tension consequent to harmonic disturbances of surface area, for samples of cloud-water and of aerosol dissolved in water. The oscillating-air-bubble tensiometer appears a suitable instrument for the assessment of the ‘availability to the air–water interface’ of natural and man-made adsorption-film-forming organic materials, present in the atmosphere.