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.

Non-local fluctuation phenomena in liquids.

Fluids in non-equilibrium steady states exhibit long-range fluctuations which extend over the entire system. They can be described by non-equilibrium thermodynamics and fluctuating hydrodynamics that assume local equilibrium for the thermophysical properties as a function of space and time. The experimental evidence for the consistency between this assumption of local equilibrium in the equations and the non-local fluctuation phenomena observed is reviewed.

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.

Note: Quasi-real-time analysis of dynamic near field scattering data using a graphics processing unit.

We present an implementation of the analysis of dynamic near field scattering (NFS) data using a graphics processing unit. We introduce an optimized data management scheme thereby limiting the number of operations required. Overall, we reduce the processing time from hours to minutes, for typical experimental conditions. Previously the limiting step in such experiments, the processing time is now comparable to the data acquisition time. Our approach is applicable to various dynamic NFS methods, including shadowgraph, Schlieren and differential dynamic microscopy.

Photon correlation spectroscopy with incoherent light.

Photon correlation spectroscopy (PCS) is based on measuring the temporal correlation of the light intensity scattered by the investigated sample. A typical setup requires a temporally coherent light source. Here, we show that a short-coherence light source can be used as well, provided that its coherence properties are suitably modified. This results in a "skewed-coherence" light beam allowing that restores the coherence requirements. This approach overcomes the usual need for beam filtering, which would reduce the total brightness of the beam.

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.

Characterization of anisotropic nano-particles by using depolarized dynamic light scattering in the near field.

Light scattering techniques are widely used in many fields of condensed and soft matter physics. Usually these methods are based on the study of the scattered light in the far field. Recently, a new family of near field detection schemes has been developed, mainly for the study of small angle light scattering. These techniques are based on the detection of the light intensity near to the sample, where light scattered at different directions overlaps but can be distinguished by Fourier transform analysis. Here we report for the first time data obtained with a dynamic near field scattering instrument, measuring both polarized and depolarized scattered light. Advantages of this procedure over the traditional far field detection include the immunity to stray light problems and the possibility to obtain a large number of statistical samples for many different wave vectors in a single instantaneous measurement. By using the proposed technique we have measured the translational and rotational diffusion coefficients of rod-like colloidal particles. The obtained data are in very good agreement with the data acquired with a traditional light scattering apparatus.

Observation of the ion-mirror effect during microscopy of insulating materials.

Utilizing the ion beam of a focused ion beam (FIB)/scanning electron microscope (SEM) microscope to investigate non-conductive samples, we observe a mirror image very much similar to the one that is commonly obtained with the electron beam and the same samples. To our knowledge this is the first observation of what can be called 'Ion-Mirror Effect'. This effect is produced by a positive charging of the sample obtained by rastering with high-energy ions (30 kV) and a subsequent imaging with low energy ones (5 kV). The proposed explanation is that first a positive charge is trapped within the sample and eventually the lower energy ions are deflected back by the latter, and hit the surface of the microscope chamber very similar to what happens in the 'Electron-Mirror Effect'. The mirror image is produced after detection of the electrons produced by the interaction between ions and the chamber materials.

Modeling cross correlations within a many-assets market.

A simple model for simulating cross correlations of a many-assets market is discussed. Correlations between assets are initially considered within the context of the well-known one-factor model, in which a driving term common to all stocks is present. The results are compared to those of real market data corresponding to a set of 445 stocks taken from the Standard and Poors 500 index. The model is further extended by introducing a stochastic volatility within each time series using an autoregressive scheme. This artificial market reproduces the empirically observed fat tails in the distribution function of logarithmic price variations and, more important, leads to additional cross correlations between the time series, in better agreement with the real market behavior.