Modeling and correction of image drift in dynamic shadowgraphy experiments.

The study of phoretic transport phenomena under non-stationary conditions presents several challenges, mostly related to the stability of the experimental apparatus. This is particularly true when investigating with optical means the subtle temperature and concentration fluctuations that arise during diffusion processes, superimposed to the macroscopic state of the system. Under these conditions, the tenuous signal from fluctuations is easily altered by the presence of artifacts. Here, we address an experimental issue frequently reported in the investigation by means of dynamic shadowgraphy of the non-equilibrium fluctuations arising in liquid mixtures under non-stationary conditions, such as those arising after the imposition or removal of a thermal stress, where experiments show systematically the presence of a spurious contribution in the reconstructed structure function of the fluctuations, which depends quadratically from the time delay. We clarify the mechanisms responsible for this artifact, showing that it is caused by the imperfect alignment of the sample cell with respect to gravity, which couples the temporal evolution of the concentration profile within the sample with the optical signal collected by the shadowgraph diagnostics. We propose a data analysis protocol that enables disentangling the spurious contributions and the genuine dynamics of the fluctuations, which can be thus reliably reconstructed.

Dynamics of non-equilibrium concentration fluctuations during free-diffusion in highly stratified solutions of glycerol and water.

We investigate the non-equilibrium fluctuations occurring during free diffusion between two solutions of glycerol and water with various concentration differences. The non-linearity of the system, determined by the strong stratification of the sample, requires introducing an interpretation model able to characterize the dependence of the correlation properties of the non-equilibrium fluctuations on the local thermophysical variables of the system. The proposed model allows us to characterize the dynamics of non-equilibrium fluctuations in the presence of a wide range of relaxation times determined by the strong stratification of the sample, at variance with the cumulant methods commonly used in dynamic light scattering experiments, which work well in the presence of a moderate dispersion of relaxation times.

Stabilized convection in a ternary mixture with two Soret coefficients of opposite sign.

We performed ground-based experiments on the sample polystyrene-toluene-cyclohexane in order to complement the experimental activities in microgravity conditions related to the ESA projects DCMIX4 and Giant Fluctuations. After applying a stabilizing thermal gradient by heating from above a layer of the fluid mixture, we studied over many hours the density variations in the bidimensional horizontal field by means of a Shadowgraph optical setup. The resulting images evidence the appearance of convective instability after a diffusive time associated with the binary molecular solvent consisting of toluene and cyclohexane, confirming the negative sign of the Soret coefficient of this mixture. After a larger diffusive time related to mass diffusion of the polystyrene in the binary solvent, convection was suppressed by the increasing stabilizing density gradient originated by the Soret-induced concentration gradient of the polymer. This is compatible with a positive sign of the Soret coefficient of the polymer in the binary solvent.

Diffusion and convection in nature.

We present the Topical Issue 'Diffusion and Convection in Nature'.

The modern structurator: increased performance for calculating the structure function.

The autocorrelation function is a statistical tool that is often combined with dynamic light scattering (DLS) techniques to investigate the dynamical behavior of the scattered light fluctuations in order to measure, for example, the diffusive behavior of transparent particles dispersed in a fluid. An alternative approach to the autocorrelation function for the analysis of DLS data has been proposed decades ago and consists of calculating the autocorrelation function starting from difference of the signal at different times by using the so-called structure function. The structure function approach has been proven to be more robust than the autocorrelation function method in terms of noise and drift rejection. Therefore, the structure function analysis has gained visibility, in particular in combination with imaging techniques such as dynamic shadowgraphy and differential dynamic microscopy. Here, we show how the calculation of the structure function over thousands of images, typical of such techniques, can be accelerated, with the aim of achieving real-time analysis. The acceleration is realized by taking advantage of the Wiener-Khinchin theorem, i.e., by calculating the difference of images through Fourier transform in time. The new algorithm was tested both on CPU and GPU hardware, showing that the acceleration is particularly large in the case of CPU.

Spreading of infections on random graphs: A percolation-type model for COVID-19.

We introduce an epidemic spreading model on a network using concepts from percolation theory. The model is motivated by discussing the standard SIR model, with extensions to describe effects of lockdowns within a population. The underlying ideas and behaviour of the lattice model, implemented using the same lockdown scheme as for the SIR scheme, are discussed in detail and illustrated with extensive simulations. A comparison between both models is presented for the case of COVID-19 data from the USA. Both fits to the empirical data are very good, but some differences emerge between the two approaches which indicate the usefulness of having an alternative approach to the widespread SIR model.

Cylindrical flowing-junction cell for the investigation of fluctuations and pattern-formation in miscible fluids.

We describe a flowing-junction cell with cylindrical symmetry suitable to investigate fluctuations and pattern formation at the diffusing interface between two miscible phases of a liquid mixture. The continuous outflow of the remixed fluid through a thin slit located at the midheight of the sample allows the preparation of an initially sharp interface. The system can be used in both gravity-stable and unstable conditions. In the stable case, the denser liquid is on the bottom of the cell and mass diffusion is the only active process for remixing the two liquids. Once the flow is stopped, one can investigate nonequilibrium fluctuations during free-diffusion in a binary mixture or double diffusive instabilities in multicomponent mixtures. Two horizontal transparent windows allow vertical mapping of the fluid flow by using shadowgraphy. In the unstable condition, with the denser fluid on top, stopping the radial flow at the interface gives rise to a Rayleigh-Taylor instability, which drives the denser liquid toward the bottom of the cell. The fact that the cell can maintain the system in the unstable condition shows that it is suitable to perform experiments under microgravity conditions. With respect to other free-diffusion cells, the proposed configuration has the advantage that the interface is extremely stable and flat, and that the experiments can be repeated by just flowing the cell with fresh liquids.

Asymmetric time-cross-correlation of nonequilibrium concentration fluctuations in a ternary liquid mixture.

Equilibrium phenomena are characterized by time symmetry. Thermodynamic fluctuations are also time-symmetric at equilibrium. Conversely, diffusion of a solute in a liquid in the presence of a gradient is a nonequilibrium phenomenon, which gives rise to long-range fluctuations with amplitude much larger than the equilibrium one for small enough wave number. In the case of diffusion in binary mixtures such fluctuations are time-symmetric, notwithstanding the fact that they are generated by a nonequilibrium condition. In this paper, we investigate diffusion of two solutes in a ternary liquid mixture by means of fluctuating hydrodynamics theory. We show that the time-cross-correlation function of the concentrations is not time-symmetric, hence showing that time symmetry is violated for such nonequilibrium fluctuations. We discuss the feasibility of experiments aimed at the detection of the asymmetry of the cross-correlation function of nonequilibrium concentration fluctuations in ternary mixtures, as envisaged in the Giant Fluctuations (NEUF-DIX) microgravity project of the European Space Agency.

Kinetics of growth of non-equilibrium fluctuations during thermodiffusion in a polymer solution.

A thermal diffusion process occurring in a binary liquid mixture is accompanied by long ranged non-equilibrium concentration fluctuations. The amplitude of these fluctuations at large length scales can be orders of magnitude larger than that of equilibrium ones. So far non-equilibrium fluctuations have been mainly investigated under stationary or quasi-stationary conditions, a situation that allows to achieve a detailed statistical characterization of their static and dynamic properties. In this work we investigate the kinetics of growth of non-equilibrium concentration fluctuations during a transient thermodiffusion process, starting from a configuration where the concentration of the sample is uniform. The use of a large molecular weight polymer solution allows to attain a slow dynamics of growth of the macroscopic concentration profile. We focus on the development of fluctuations at small wave vectors, where their amplitude is strongly limited by the presence of gravity. We show that the growth rate of non-equilibrium fluctuations follows a power law [Formula: see text] as a function of time, without any typical time scale and independently of the wave vector. We formulate a phenomenological model that allows to relate the rate of growth of non-equilibrium fluctuations to the growth of the macroscopic concentration profile in the absence of arbitrary parameters.

Propagating modes in a binary liquid mixture under thermal stress.

Nonequilibrium temperature and concentration fluctuations inside a binary liquid mixture under the action of a temperature gradient relax back to equilibrium either due to conduction and diffusion at large wave numbers, or due to the quenching determined by gravity at small wave numbers. We investigate the dynamics of nonequilibrium fluctuations in a binary liquid mixture of polystyrene and toluene heated from above under stationary conditions in a thermodiffusion experiment. We show that the strong gravitational stabilization at small wave numbers determines the appearance of propagating modes of nonequilibrium fluctuations as detected through the structure function of shadowgraph images. The propagating modes are the combined effect of temperature and velocity nonequilibrium fluctuations induced by the buoyancy force. The experimental results are in good agreement with a fluctuating hydrodynamics theroretical model including the coupling of fluctuations of velocity, temperature and concentration.

Thermodiffusion in multicomponent n-alkane mixtures.

Compositional grading within a mixture has a strong impact on the evaluation of the pre-exploitation distribution of hydrocarbons in underground layers and sediments. Thermodiffusion, which leads to a partial diffusive separation of species in a mixture due to the geothermal gradient, is thought to play an important role in determining the distribution of species in a reservoir. However, despite recent progress, thermodiffusion is still difficult to measure and model in multicomponent mixtures. In this work, we report on experimental investigations of the thermodiffusion of multicomponent n-alkane mixtures at pressure above 30 MPa. The experiments have been conducted in space onboard the Shi Jian 10 spacecraft so as to isolate the studied phenomena from convection. For the two exploitable cells, containing a ternary liquid mixture and a condensate gas, measurements have shown that the lightest and heaviest species had a tendency to migrate, relatively to the rest of the species, to the hot and cold region, respectively. These trends have been confirmed by molecular dynamics simulations. The measured condensate gas data have been used to quantify the influence of thermodiffusion on the initial fluid distribution of an idealised one dimension reservoir. The results obtained indicate that thermodiffusion tends to noticeably counteract the influence of gravitational segregation on the vertical distribution of species, which could result in an unstable fluid column. This confirms that, in oil and gas reservoirs, the availability of thermodiffusion data for multicomponent mixtures is crucial for a correct evaluation of the initial state fluid distribution.

Soret coefficient of the n-dodecane-n-hexane binary mixture under high pressure.

In the present work, the Soret coefficient has been determined at high pressure for a binary hydrocarbon mixture by combining the thermogravitational column and the dynamic near-field imaging techniques. The analyzed mixture is an iso-massic n -dodecane-n -hexane mixture at 298.15K. The molecular diffusion coefficient has been measured up to 20MPa by means of the dynamic analysis of the light scattered by non-equilibrium concentration fluctuations. With a cylindrical thermogravitational column the thermodiffusion coefficient was determined from 0.1MPa to 10MPa. Density, as well as, mass expansion and thermal expansion have been measured with a high pressure densimeter. Dynamic viscosity at up to 20MPa has been determined with a high pressure viscometer. This work shows the decreasing tendency of both the molecular diffusion and the thermodiffusion coefficient with increasing pressure.

Dynamic analysis of the light scattered by the non-equilibrium fluctuations of a ternary mixture of polystyrene-toluene-n-hexane.

Dynamic analysis of the light scattered by non-equilibrium fluctuations in a thermodiffusion experiment has been performed on a sample of polystyrene-toluene-n -hexane, at 0.9-49.55-49.55% mass fraction. Time decays of the non-equilibrium fluctuations have been obtained revealing the accurate detectability of three modes. The slowest mode has been attributed to the mass diffusion of the polymer into the binary solvent; the intermediate one to mass diffusion of the two molecular components of the solvent; finally, the fastest one has been attributed to the thermal diffusivity of the overall mixture. The two eigenvalues of the mass diffusion matrix have been evaluated with accuracy in the order of 1%. Neglecting cross-diffusion effects we obtain a simplified expression for the relative amplitude of the two mass diffusion modes, allowing a parameterized determination of polystyrene and toluene Soret coefficients in the ternary mixture. We suggest that a two wavelength shadowgraph experiment is needed for a complete determination of all the coefficients.

Gravity effects on Soret-induced non-equilibrium fluctuations in ternary mixtures.

We discuss the gravity effects on the dynamics of composition fluctuations in a ternary mixture around the non-equilibrium quiescent state induced by thermodiffusion when subjected to a stationary temperature gradient. We found that the autocorrelation matrix of concentration fluctuations can be expressed as the sum of two exponentially decaying concentration modes. Without accounting for confinement, we obtained exact analytical expressions for the two decay rates which, as a consequence of gravity, display a wave-number-dependent mixing. The stability of the quiescent solution is also examined, as a function of the two solutal Rayleigh numbers used to express the decay rates. After having discussed the dynamics of the two concentration modes, we calculate the corresponding amplitudes. Consequences for optical experiments are discussed.

Non-equilibrium concentration fluctuations in superparamagnetic nanocolloids.

We investigate non-equilibrium concentration fluctuations during the free diffusion of a colloidal suspension against pure water. We investigate Fe2O3 superparamagnetic nanocolloids with sizes between 1 and 10 nm by means of a shadowgraph apparatus to determine the mixture mass diffusion coefficient and kinematic viscosity. The experiments were performed in three distinct conditions: Experiment 1 is without any magnetic field; Experiment 2 with a vertical magnetic field; Experiment 3 after turning off the magnetic field. We found no correlation between the kinematic viscosity coefficient and the external magnetic field. Conversely, we found that the mass diffusion coefficient decreases in the presence of the external magnetic field and slowly rebounds after the magnetic field was turned off.

Confinement effect on the dynamics of non-equilibrium concentration fluctuations far from the onset of convection.

In a recent letter (C. Giraudet et al., EPL 111, 60013 (2015)) we reported preliminary data showing evidence of a slowing-down of non-equilibrium fluctuations of the concentration in thermodiffusion experiments on a binary mixture of miscible fluids. The reason for this slowing-down was attributed to the effect of confinement. Such tentative explanation is here experimentally corroborated by new measurements and theoretically substantiated by studying analytically and numerically the relevant fluctuating hydrodynamics equations. In the new experiments presented here, the magnitude of the temperature gradient is changed, confirming that the system is controlled solely by the solutal Rayleigh number, and that the slowing-down is dominated by a combined effect of the driving force of buoyancy, the dissipating force of diffusion and the confinement provided by the vertical extension of the sample cell. Moreover, a compact phenomenological interpolating formula is proposed for easy analysis of experimental results.

Microgravity in a thin film: How confinement kills gravity.

Fluctuations in the presence of concentration gradients are long-ranged and decay diffusively for small spatial scales. At larger scales fluctuations are influenced by gravity and confinement. The confinement in the direction of the concentration gradient couples to gravity generating a slowing down that ends up in a diffusion-like behavior of fluctuations of size comparable to the vertical extension of the sample. The resulting enhanced diffusion coefficient depends on the solutal Rayleigh number of the system. For small (in modulus) values of the solutal Rayleigh number the apparent diffusion coefficient tends towards the normal one and a simple diffusive behavior is obtained. This is quite similar to what happens in microgravity conditions when the solutal Rayleigh number is drastically reduced because of the reduction of g by about 6 orders of magnitude. Experiments are shown for positive and negative solutal Rayleigh numbers smaller (in modulus) than 1000. The effect of the confinement on the statics is also investigated. Comparison with microgravity data obtained through the GRADFLEX project is performed.