Sandra J. Veen

Colloidal aggregation in microgravity by critical Casimir forces

By using the critical Casimir force, we study the attractive strength dependent aggregation of colloids with and without gravity by means of near field scattering. Significant differences were seen between microgravity and ground experiments, both in the structure of the formed fractal aggregates as well as in the kinetics of growth. In microgravity purely diffusive aggregation is observed. By using the continuously variable particle interaction potential we can for the first time experimentally relate the strength of attraction between the particles and the structure of the aggregates.

SODI-COLLOID: a combination of static and dynamic light scattering on board the International Space Station

Microgravity research in space is a complex activity where the often scarce resources available for the launch, accommodation, and operation of instrumentation call for a careful experiment planning and instrument development. In this paper we describe a module of the Selectable Optical Diagnostic Instrument, that has been designed as a compact optical diagnostic instrument for colloidal physics experiments. The peculiarity of the instrument is the combination of a novel light scattering technique known as near field scattering and standard microscopy with a low-coherence laser light source. We describe its main design features, as well as measurement results on colloidal aggregation taken on the International Space Station.

Phase transitions in cellulose microfibril dispersions by high-energy mechanical deagglomeration.

It is shown that dispersions of cellulose microfibrils display gel-sol and direct gel-colloidal liquid crystalline structure transitions. This is achieved by applying high-energy mechanical deagglomeration to bacterial cellulose (BC) networks in the presence of sodium carboxymethyl cellulose (CMC). At high CMC content adsorption of the polymer leads to a significant increase in the ζ potential. The resulting apparent phase diagram shows transitions from aggregates to single microfibril dispersions with increasing the CMC/BC weight ratio at low microfibril concentrations. At higher concentrations, liquid crystalline ordering was observed and the microstructure becomes more homogeneous with increasing the CMC content. The observed liquid crystalline ordering was found to be reminiscent of nematic gels. Applying deagglomeration in the presence of CMC, thus, transitions the system from aggregates and gels to dispersions of single microfibrils and nematic gel-type structures.

Extended Structure Design with Simple Molybdenum Oxide Building Blocks and Urea As a Directing Agent

We report here a simple one-pot directed synthesis of an oxomolybdate urea composite in which elementary molybdenum oxide building blocks are linked together with the aid of urea. This type of directed material design resulted in large rod-like crystals of an inorganic-organic hybrid extended structure of {MoO 3(NH 2-CO-NH 2)} infinity consisting of right- and left-handed helical units. In the crystal structure urea acts both as a glue that links the inorganic molybdenum units into a helix and as a supramolecular linker for the stabilization of the crystal structure as a whole. This type of molecular topology resulted in an unexpectedly high thermal stability.

Switching Colloidal Superstructures by Critical Casimir Forces

Recent breakthroughs in colloidal synthesis promise the bottom-up assembly of superstructures on nano- and micrometer length scales, offering molecular analogues on the colloidal scale. However, a structural control similar to that in supramolecular chemistry remains very challenging. Here, colloidal superstructures are built and controlled using critical Casimir forces on patchy colloidal particles. These solvent-mediated forces offer direct analogues of molecular bonds, allowing patch-to-patch binding with exquisite temperature control of bond strength and stiffness. Particles with two patches are shown to form linear chains undergoing morphological changes with temperature, resembling a polymer collapse under poor-solvent conditions. This reversible temperature switching carries over to particles with higher valency, exhibiting a variety of patch-to-patch bonded structures. Using Monte Carlo simulations, it is shown that the collapse results from the growing interaction range favoring close-packed configurations. These results offer new opportunities for the active control of complex structures at the nano and micrometer scale, paving the way to novel temperature-switchable materials.

Dynamics of colloidal aggregation in microgravity by critical Casimir forces

By combining static and dynamic structure factor measurements under microgravity conditions, we obtain for the first time direct insight into the internal structure of colloidal aggregates formed over a wide range of particle attractions under ideal diffusion-limited conditions. By means of near-field scattering we measure the time-dependent density-density correlation function as the aggregation process evolves, and we determine the ratio of the hydrodynamic and gyration radius to elucidate the aggregates internal structure as a function of its fractal dimension. Surprisingly, we find that despite the large variation of particle interactions, the mass is always evenly distributed in all objects with fractal dimension ranging from 2.55 for shallow potentials to 1.78 for deep ones.

Structural instability of shell-like assemblies of a keplerate-type polyoxometalate induced by ionic strength

We demonstrate a new structural instability of shell-like assemblies of polyoxometalates. Besides the colloidal instability, that is, the formation of aggregates that consist of many single layered POM-shells, these systems also display an instability on a structural scale within the shell-like assemblies. This instability occurs at significantly lower ionic strength than the colloidal stability limit and only becomes evident after a relatively long time. For the polyoxometalate, abbreviated as {Mo(72)Fe(30)}, it is shown that the structural stability limit of POM-shells lies between a NaCl concentration of 1.00 and 5.00 mM in aqueous solution.

Revealing and Quantifying the Three-Dimensional Nano- and Microscale Structures in Self-Assembled Cellulose Microfibrils in Dispersions

Cellulose microfibrils (CMFs) are an important nanoscale building block in many novel biobased functional materials. The spatial nano- and microscale organization of the CMFs is a crucial factor for defining the properties of these materials. Here, we report for the first time a direct three-dimensional (3D) real-space analysis of individual CMFs and their networks formed after ultrahigh-shear-induced transient deagglomeration and self-assembly in a solvent. Using point-scanning confocal microscopy combined with tracking the centerlines of the fibrils and their junctions by a stretching open active contours method, we reveal that dispersions of the native CMFs assemble into highly heterogeneous networks of individual fibrils and bundles. The average network mesh size decreases with increasing CMF volume fraction. The cross-sectional width and the average length between the twists in the ribbon-shaped CMFs are directly determined and compared well with that of fibrils in the dried state. Finally, the generality of the fluorescent labeling and imaging approach on other CMF sources is illustrated. The unique ability to quantify in situ the multiscale structure in CMF dispersions provides a powerful tool for the correlation of process–structure–property relationship in cellulose-containing composites and dispersions.