Diffusion in liquid mixtures.

The understanding of transport and mixing in fluids in the presence and in the absence of external fields and reactions represents a challenging topic of strategic relevance for space exploration. Indeed, mixing and transport of components in a fluid are especially important during long-term space missions where fuels, food and other materials, needed for the sustainability of long space travels, must be processed under microgravity conditions. So far, the processes of transport and mixing have been investigated mainly at the macroscopic and microscopic scale. Their investigation at the mesoscopic scale is becoming increasingly important for the understanding of mass transfer in confined systems, such as porous media, biological systems and microfluidic systems. Microgravity conditions will provide the opportunity to analyze the effect of external fields and reactions on optimizing mixing and transport in the absence of the convective flows induced by buoyancy on Earth. This would be of great practical applicative relevance to handle complex fluids under microgravity conditions for the processing of materials in space.

Mass diffusion and Soret coefficient measurements of triethylene glycol/water binary mixtures by dynamic shadowgraphy.

The investigation of the transport properties of binary fluid mixtures remains a topic of interest in relation to the more challenging studies of ternary mixtures. In fact, the study of the phase boundary limits of the Gibbs composition triangle can be the initial step for a more complete analysis of ternary mixtures. In this paper, we apply the dynamic shadowgraphy optical technique to study non-equilibrium fluctuations induced by the presence of a gradient of temperature and/or concentration in the triethylene glycol (TEG)/water system. These thermodiffusion and free-diffusion experiments aim at measuring the transport properties of samples of the studied system at different experimental conditions. We scan both the average temperature and the TEG concentration, which allows us investigating both positive and negative thermodiffusive behaviours. The obtained values of mass diffusion coefficient are consistent with data available in the literature in the range of temperature investigated in this study. The mass diffusion coefficient of the sample prepared at 0.7 w/w TEG concentration are characterised by shadowgraphy following the two proposed methods, exhibiting consistent results. An increase of the mass diffusion coefficient as a function of the average temperature is highlighted. On the other hand, the thermodiffusion coefficient appears to be independent of the average temperature of the sample at 0.3 w/w TEG concentration.

The Soret coefficients of the ternary system water/ethanol/triethylene glycol and its corresponding binary mixtures.

Thermodiffusion in ternary mixtures is considered prototypic for the Soret effect of truly multicomponent systems. We discuss ground-based measurements of the Soret coefficient along the binary borders of the Gibbs triangle of the highly polar and hydrogen bonding ternary DCMIX3-system water/ethanol/triethylene glycol. All three Soret coefficients decay with increasing concentration, irrespective of the choice of the independent component, and show a characteristic sign change as a function of temperature and/or composition. With the exception of triethylene glycol/ethanol at high temperatures, the minority component always migrates toward the cold side. All three binaries exhibit temperature-independent fixed points of the Soret coefficient. The decay of the Soret coefficient with concentration can be related to negative excess volumes of mixing. The sign changes of the Soret coefficients of the binaries allow to draw far-reaching conclusions about the signs of the Soret coefficients of the corresponding ternary mixtures. In particular, we show that at least one ternary composition must exist, where all three Soret coefficients vanish simultaneously and no steady-state separation is observable.

Coupled non-equilibrium fluctuations in a polymeric ternary mixture.

We investigate by dynamic shadowgraphy the non-equilibrium fluctuations at the steady state of a thermodiffusion experiment in a polymeric ternary mixture of polystyrene-toluene-n-hexane. The structure function of the refractive index reveals the existence of quite different decay times, thus requiring the analysis of a wide range of correlation times. This is related to the simultaneous presence of three distinct decay modes corresponding to (from fastest to slowest) the relaxation of temperature fluctuations, of the concentration fluctuations of the mixed solvent, and of the concentration fluctuations of the polymer in the binary solvent. An investigation of the decay times at the corresponding diffusive regimes provides a measurement of the thermal diffusivity and the two eigenvalues of the mass diffusion matrix of the ternary mixture. Similar experiments were performed in the past but here, to suppress the confinement effect and obtain a more direct comparison with the theory, a thicker sample is studied. Moreover, also a faster camera is used allowing the experimental observation of faster modes, like the propagative ones. The experimental values of the decay times are eventually compared with those predicted by different available theories. Finally, we present a more complete theoretical model to describe the non-equilibrium fluctuations in the bulk of a ternary mixture at the steady state of a thermodiffusion experiment.

European Space Agency experiments on thermodiffusion of fluid mixtures in space.

This paper describes the European Space Agency (ESA) experiments devoted to study thermodiffusion of fluid mixtures in microgravity environment, where sedimentation and convection do not affect the mass flow induced by the Soret effect. First, the experiments performed on binary mixtures in the IVIDIL and GRADFLEX experiments are described. Then, further experiments on ternary mixtures and complex fluids performed in DCMIX and planned to be performed in the context of the NEUF-DIX project are presented. Finally, multi-component mixtures studied in the SCCO project are detailed.

Preliminary analysis of Diffusion Coefficient Measurements in ternary mIXtures 4 (DCMIX4) experiment on board the International Space Station.

In the frame of the Diffusion Coefficient Measurements in ternary mIXtures 4 (DCMIX4) project the thermodiffusion experiments were conducted on the International Space Station (ISS) in the Selectable Optical Diagnostics Instrument (SODI) which is on orbit since 2009. We describe the results of the preliminary analysis of images downloaded during the execution of DCMIX4 in order to check the quality of the running experiments and, if needed, adjust the experiment parameters for the following runs. The quick analysis of raw data showed that they are meaningful and will allow to obtain the transport coefficients of examined ternary and binary mixtures.

Concentration dependent refractive index of CO2/CH4 mixture in gaseous and supercritical phase.

Carbon dioxide (CO2)/methane (CH4) binary mixtures are investigated at pressure values up to 20 MPa at 303 K in order to investigate the pressure dependence of the optical concentration contrast factor, ∂n/∂c(P,T), through gaseous and supercritical phase. Refractive index is measured by means of a Michelson interferometer. Refractivities of the mixtures are found in good agreement with Lorentz-Lorenz predictions after density calculations by means of the AGA8-DC92 equation of state. Experimental polarizabilities of pure fluids are compared to quantum calculations of monomers and dimers for each pressure; it results that the quantity of dimers is small in the investigated thermodynamic conditions. Finally, by extending our experimental database with numerical simulations, we evidence that ∂n/∂cP,T presents a critical enhancement similar to heat capacity.

High-pressure mass transport properties measured by dynamic near-field scattering of non-equilibrium fluctuations.

High-pressure mass diffusion and Soret coefficients of the equimassic 1,2,3,4-tetrahydronaphthalene and n-dodecane binary mixture are obtained from dynamic light scattering analysis of concentration non-equilibrium fluctuations at the steady state of Soret-driven separation. A high-pressure shadowgraph set-up has been developed to investigate thermodiffusion in free medium from atmospheric pressure up to 20 MPa. Results at atmospheric pressure show excellent agreement with benchmark values. High-pressure results for the mass diffusion coefficient confirm theoretical predictions by Leffler-Cullinan relation. Further calculation of the thermodiffusion coefficient allows also comparison with previous experimental results with, again, very good agreement.

A light scattering study of non equilibrium fluctuations in liquid mixtures to measure the Soret and mass diffusion coefficient.

We use dynamic near field scattering to measure the dynamics of concentration non equilibrium fluctuations at the steady-state of Soret separation. The analysis reveals that above a threshold wave vector q(c), the dynamics is governed by diffusion while at smaller wave vectors, gravity dominates. From the measurements, we extract both the mass diffusion and the Soret coefficients. Comparing our results with literature data, we find good agreement confirming that the proposed experimental technique can be considered a sound approach for the study of thermodiffusion processes.

Measurement of thermodiffusion coefficient of hydrocarbon binary mixtures under pressure with the thermogravitational technique.

It was designed and constructed a new thermogravitational column able to operate at high pressures (up to 50 MPa). This new thermogravitational column is of the cylindrical type with closed ends. It is made of stainless steel. The length of the column is 0.5 m and the gap between its two walls is variable. First, the column was validated at atmospheric pressure by means of measurements of the thermodiffusion coefficient of well-known binary mixtures. Then, this new thermogravitational column was used to measure the thermodiffusion coefficient of the binary mixtures 1,2,3,4-tetrahydronaphtalene/isobutylbenzene, 1,2,3,4-tetrahydronaphtalene/n-dodecane, and isobutylbenzene/n-dodecane at high pressures and within the pressure range between 0.1 and 20 MPa at a mean temperature of 25 °C. We have found a linear dependence between the thermodiffusion coefficient and the pressure.

Note: Temperature derivative of the refractive index of binary mixtures measured by using a new thermodiffusion cell.

A thermodiffusion cell is developed for performing Soret experiments on binary mixtures at high pressure and in the presence of a porous medium. The cell is validated by performing experiments at atmospheric pressure. The experiments are performed by applying different temperature gradients to binary mixtures in order to determine their thermal contrast factor. These measurements provide a first demonstration of the good reproducibility of this kind of measurements upon calibration.