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.

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.

Microliter viscometry using a bright-field microscope: η-DDM.

The rheological properties of a medium can be inferred from the Brownian motion of colloidal tracer particles using the microrheology procedure. The tracer motion can be characterized by the mean-squared displacement (MSD). It can be calculated from the intermediate scattering function determined by Differential Dynamic Microscopy (DDM). Here we show that DDM together with the empirical Cox-Merz rule is particularly suited to measure the steady-shear viscosity, i.e. the viscosity towards zero frequency, due to its ability to provide reliable information on long time and length scales and hence small frequencies. This method, η-DDM, is tested and illustrated using three different systems: Newtonian fluids (glycerol-water mixtures), colloidal suspensions (protein samples) and a viscoelastic polymer solution (aqueous poly(ethylene oxide) solution). These tests show that common lab equipment, namely a bright-field optical microscope, can be used as a convenient and reliable microliter viscometer. Because η-DDM requires much smaller sample volumes than classical rheometry, only a few microliters, it is particularly useful for biological and soft matter systems.

Dense colloidal mixtures in an external sinusoidal potential.

Concentrated binary colloidal mixtures containing particles with a size ratio 1:2.4 were exposed to a periodic potential that was realized using a light field, namely, two crossed laser beams creating a fringe pattern. The arrangement of the particles was recorded using optical microscopy and characterized in terms of the pair distribution function along the minima, the occupation probability perpendicular to the minima, the angular bond distribution, and the average potential energy per particle. The particle arrangement was investigated in dependence of the importance of particle-potential and particle-particle interactions by changing the potential amplitude and particle concentration, respectively. An increase in the potential amplitude leads to a stronger localization, especially of the large particles, but also results in an increasing fraction of small particles being located closer to the potential maxima, which also occurs upon increasing the particle density. Furthermore, increasing the potential amplitude induces a local demixing of the two particle species, whereas an increase in the total packing fraction favors a more homogeneous arrangement.

Investigation of moderately turbid suspensions by heterodyne near field scattering.

Light scattering has proven to be a very powerful technique to characterize soft matter systems. However, many samples are turbid and hence suffer from multiple scattering which can affect the signal considerably. Multiple scattering can be reduced by diluting the sample or changing the solvent, but often this alters the sample and hence is precluded. Here we study the dynamics of a model system. In particular, we investigate the effects of moderate multiple scattering on small-angle heterodyne near field scattering (HNFS). Varying the particle concentration and size we change the degree of multiple scattering, which is quantified by the transmission of light. In dependence of the degree of multiple scattering, we analyze the statistical properties of the HNFS signal, which is the difference between two intensity patterns separated by a delay time. The distribution of intensity differences follows a Gaussian distribution if single scattering dominates and a Laplace distribution in the presence of extreme multiple scattering. We also investigate the effects of multiple scattering on the measured intermediate scattering function and the hydrodynamic radius of the particles. Reliable data are obtained for sample transmissions down to about 0.7. This is confirmed by a comparison with results from a far field cross-correlation instrument that suppresses multiple scattering contributions. Therefore, HNFS represents a technically simple but powerful method to investigate samples that are moderately multiple scattering.

Note: Using a Kösters prism to create a fringe pattern.

The interference of two crossed laser beams results in a standing wave. Such fringe patterns are exploited in different instruments such as interferometers or laser-Doppler anemometers. We create a fringe pattern in the sample plane of a microscope using a compact apparatus based on a Kösters prism. The fringe pattern is shown to be spatially and temporally very stable, covers a large area, and its spacing is easily tunable. In addition, we exploit it to impose a sinusoidal potential on colloidal particles.

Long-Lived Neighbors Determine the Rheological Response of Glasses.

Glasses exhibit a liquidlike structure but a solidlike rheological response with plastic deformations only occurring beyond yielding. Thus, predicting the rheological behavior from the microscopic structure is difficult, but important for materials science. Here, we consider colloidal suspensions and propose to supplement the static structural information with the local dynamics, namely, the rearrangement and breaking of the cage of neighbors. This is quantified by the mean squared nonaffine displacement and the number of particles that remain nearest neighbors for a long time, i.e., long-lived neighbors, respectively. Both quantities are followed under shear using confocal microscopy and are the basis to calculate the affine and nonaffine contributions to the elastic stress, which is complemented by the viscoelastic stress to give the total stress. During start-up of shear, the model predicts three transient regimes that result from the interplay of affine, nonaffine, and viscoelastic contributions. Our prediction quantitatively agrees with rheological data and their dependencies on volume fraction and shear rate.

Triple Junction at the Triple Point Resolved on the Individual Particle Level.

At the triple point of a repulsive screened Coulomb system, a fcc crystal, a bcc crystal, and a fluid phase coexist. At their intersection, these three phases form a liquid groove, the triple junction. Using confocal microscopy, we resolve the triple junction on a single-particle level in a model system of charged PMMA colloids in a nonpolar solvent. The groove is found to be extremely deep and the incommensurate solid-solid interface to be very broad. Thermal fluctuations hence appear to dominate the solid-solid interface. This indicates a very low interfacial energy. The fcc-bcc interfacial energy is quantitatively determined based on Young's equation and, indeed, it is only about 1.3 times higher than the fcc-fluid interfacial energy close to the triple point.

Size-Dependent Localization in Polydisperse Colloidal Glasses.

We have investigated concentrated suspensions of polydisperse hard spheres and have determined the dynamics and sizes of individual particles using confocal microscopy. With increasing concentration, the dynamics of the small and large particles start to differ. The large particles exhibit slower dynamics and stronger localization. Moreover, as the particle size increases, the local volume fraction ϕ_{loc} also increases. In the glass state, the localization length significantly decreases beyond ϕ_{loc}≈0.67. This suggests a link between local crowding and dynamical heterogeneities. However dynamical arrest of subpopulations seems not directly linked to a large value of ϕ_{loc}, indicating the importance of collective effects.

Directed percolation identified as equilibrium pre-transition towards non-equilibrium arrested gel states.

The macroscopic properties of gels arise from their slow dynamics and load-bearing network structure, which are exploited by nature and in numerous industrial products. However, a link between these structural and dynamical properties has remained elusive. Here we present confocal microscopy experiments and simulations of gel-forming colloid-polymer mixtures. They reveal that gel formation is preceded by continuous and directed percolation. Both transitions lead to system-spanning networks, but only directed percolation results in extremely slow dynamics, ageing and a shrinking of the gel that resembles synaeresis. Therefore, dynamical arrest in gels is found to be linked to a structural transition, namely directed percolation, which is quantitatively associated with the mean number of bonded neighbours. Directed percolation denotes a universality class of transitions. Our study hence connects gel formation to a well-developed theoretical framework, which now can be exploited to achieve a detailed understanding of arrested gels.

Solvent and solute ingress into hydrogels resolved by a combination of imaging techniques.

Using simultaneous neutron, fluorescence, and optical brightfield transmission imaging, the diffusion of solvent, fluorescent dyes, and macromolecules into a crosslinked polyacrylamide hydrogel was investigated. This novel combination of different imaging techniques enables us to distinguish the movements of the solvent and fluorescent molecules. Additionally, the swelling or deswelling of the hydrogels can be monitored. From the sequence of images, dye and solvent concentrations were extracted spatially and temporally resolved. Diffusion equations and different boundary conditions, represented by different models, were used to quantitatively analyze the temporal evolution of these concentration profiles and to determine the diffusion coefficients of solvent and solutes. Solute size and network properties were varied and their effect was investigated. Increasing the crosslinking ratio or partially drying the hydrogel was found to hinder solute diffusion due to the reduced pore size. By contrast, solvent diffusion seemed to be slightly faster if the hydrogel was only partially swollen and hence solvent uptake enhanced.

Diffusion of macromolecules in a polymer hydrogel: from microscopic to macroscopic scales.

To gain insight into the fundamental processes determining the motion of macromolecules in polymeric matrices, the dynamical hindrance of polymeric dextran molecules diffusing as probe through a polyacrylamide hydrogel is systematically explored. Three complementary experimental methods combined with Brownian dynamics simulations are used to study a broad range of dextran molecular weights and salt concentrations. While multi-parameter fluorescence image spectroscopy (MFIS) is applied to investigate the local diffusion of single molecules on a microscopic length scale inside the hydrogel, a macroscopic transmission imaging (MTI) fluorescence technique and nuclear magnetic resonance (NMR) are used to study the collective motion of dextrans on the macroscopic scale. These fundamentally different experimental methods, probing different length scales of the system, yield long-time diffusion coefficients for the dextran molecules which agree quantitatively. The measured diffusion coefficients decay markedly with increasing molecular weight of the dextran and fall onto a master curve. The observed trends of the hindrance factors are consistent with Brownian dynamics simulations. The simulations also allow us to estimate the mean pore size for the herein investigated experimental conditions. In addition to the diffusing molecules, MFIS detects temporarily trapped molecules inside the matrix with diffusion times above 10 ms, which is also confirmed by anisotropy analysis. The fraction of bound molecules depends on the ionic strength of the solution and the charge of the dye. Using fluorescence intensity analysis, also MTI confirms the observation of the interaction of dextrans with the hydrogel. Moreover, pixelwise analysis permits to show significant heterogeneity of the gel on the microscopic scale.

Water ingress into a casein film quantified using time-resolved neutron imaging.

The migration of water into a casein film was probed with neutron radiography. From the neutron transmission images, the evolution of the water saturation profiles was extracted. The results indicate that the water influx is dominated by imbibition but also contains a diffusional component. The time dependence of the water ingress was quantified using a diffusion-like equation previously also applied to imbibition. A water transport coefficient D = 0.9 × 10(-9) m(2) s(-1) was found. This value and direct observation of the images indicate that the time taken for a typical adhesive casein-based layer to become saturated with water is of the order of hours.

Neutron, fluorescence, and optical imaging: An in situ combination of complementary techniques.

An apparatus which enables the simultaneous combination of three complementary imaging techniques, optical imaging, fluorescence imaging, and neutron radiography, is presented. While each individual technique can provide information on certain aspects of the sample and their time evolution, a combination of the three techniques in one setup provides a more complete and consistent data set. The setup can be used in transmission and reflection modes and thus with optically transparent as well as opaque samples. Its capabilities are illustrated with two examples. A polymer hydrogel represents a transparent sample and the diffusion of fluorescent particles into and through this polymer matrix is followed. In reflection mode, the absorption of solvent by a nile red-functionalized mesoporous silica powder and the corresponding change in fluorescent signal are studied.

Creep and flow of glasses: strain response linked to the spatial distribution of dynamical heterogeneities.

Mechanical properties are of central importance to materials sciences, in particular if they depend on external stimuli. Here we investigate the rheological response of amorphous solids, namely colloidal glasses, to external forces. Using confocal microscopy and computer simulations, we establish a quantitative link between the macroscopic creep response and the microscopic single-particle dynamics. We observe dynamical heterogeneities, namely regions of enhanced mobility, which remain localized in the creep regime, but grow for applied stresses leading to steady flow. These different behaviors are also reflected in the average particle dynamics, quantified by the mean squared displacement of the individual particles, and the fraction of active regions. Both microscopic quantities are found to be proportional to the macroscopic strain, despite the non-equilibrium and non-linear conditions during creep and the transient regime prior to steady flow.

Crystallization seeds favour crystallization only during initial growth.

Crystallization represents the prime example of a disorder-order transition. In realistic situations, however, container walls and impurities are frequently present and hence crystallization is heterogeneously seeded. Rarely the seeds are perfectly compatible with the thermodynamically favoured crystal structure and thus induce elastic distortions, which impede further crystal growth. Here we use a colloidal model system, which not only allows us to quantitatively control the induced distortions but also to visualize and follow heterogeneous crystallization with single-particle resolution. We determine the sequence of intermediate structures by confocal microscopy and computer simulations, and develop a theoretical model that describes our findings. The crystallite first grows on the seed but then, on reaching a critical size, detaches from the seed. The detached and relaxed crystallite continues to grow, except close to the seed, which now prevents crystallization. Hence, crystallization seeds facilitate crystallization only during initial growth and then act as impurities.

Different mechanisms for dynamical arrest in largely asymmetric binary mixtures.

Using confocal microscopy we investigate binary colloidal mixtures with large size asymmetry, in particular the formation of dynamically arrested states of the large spheres. The volume fraction of the system is kept constant, and as the concentration of small spheres is increased we observe a series of transitions of the large spheres to different arrested states: an attractive glass, a gel, and an asymmetric glass. These states are distinguished by the degree of dynamical arrest and the amount of structural and dynamical heterogeneity. The transitions between two different arrested states occur through melting and the formation of a fluid state. While a space-spanning network of bonded particles is found in both arrested and fluid states, only arrested states are characterized by the presence of a space-spanning network of dynamically arrested particles.

Transient dynamics during stress overshoots in binary colloidal glasses.

We investigate, using simultaneous rheology and confocal microscopy, the time-dependent stress response and transient single-particle dynamics following a step change in shear rate in binary colloidal glasses with large dynamical asymmetry and different mixing ratios. The transition from solid-like response to flow is characterised by a stress overshoot, whose magnitude is linked to transient superdiffusive dynamics as well as cage compression effects. These and the yield strain at which the overshoot occurs vary with the mixing ratio, and hence the prevailing caging mechanism. The yielding and stress storage are dominated by dynamics on different time and length scales, the short-time in-cage dynamics and the long-time structural relaxation respectively. These time scales and their relation to the characteristic time associated with the applied shear, namely the inverse shear rate, result in two different and distinct regimes of the shear rate dependencies of the yield strain and the magnitude of the stress overshoot.

Residual stresses in glasses.

The history dependence of glasses formed from flow-melted steady states by a sudden cessation of the shear rate γ[over ˙] is studied in colloidal suspensions, by molecular dynamics simulations and by mode-coupling theory. In an ideal glass, stresses relax only partially, leaving behind a finite persistent residual stress. For intermediate times, relaxation curves scale as a function of γ[over ˙]t, even though no flow is present. The macroscopic stress evolution is connected to a length scale of residual liquefaction displayed by microscopic mean-squared displacements. The theory describes this history dependence of glasses sharing the same thermodynamic state variables but differing static properties.

Transient dynamics in dense colloidal suspensions under shear: shear rate dependence.

A combination of confocal microscopy and rheology experiments, Brownian dynamics (BD) and molecular dynamics (MD) simulations and mode coupling theory (MCT) have been applied in order to investigate the effect of shear rate on the transient dynamics and stress-strain relations in supercooled and glassy systems under shear. Immediately after shear is switched on, the microscopic dynamics display super-diffusion and the macroscopic rheology a stress overshoot, which become more pronounced with increasing shear rate. MCT relates both to negative sections of the generalized shear modulus, which grow with increasing shear rate. When the inverse shear rate becomes much smaller than the structural relaxation time of the quiescent system, relaxation through Brownian motion becomes less important. In this regime, larger stresses are accumulated before the system yields and the transition from localization to flow occurs earlier and more abruptly.