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.

Microstructure and rheology of microfibril-polymer networks.

By using an adsorbing polymer in combination with mechanical de-agglomeration, the microstructure and rheological properties of networks of microfibrils could be controlled. By the addition of sodium carboxymethyl cellulose during de-agglomeration of networks of bacterial cellulose, the microstructure could be changed from an inhomogeneous network with bundles of microfibrils and voids to a more homogeneous spread and alignment of the particles. As a result the macroscopic rheological properties were altered. Although still elastic and gel-like in nature, the elasticity and viscous behavior of the network as a function of microfibril concentration is altered. The microstructure is thus changed by changing the surface properties of the building blocks leading to a direct influence on the materials macroscopic behavior.

Nematic ordering of polarizable colloidal rods in an external electric field: theory and experiment.

We employ the coupled dipole method [B. W. Kwaadgras, et al., J. Chem. Phys., 2011, 135, 134105] to calculate the orientation-dependent interaction of polarizable colloidal rods with an external electric field. We project the angular distribution function of a system of such rods on a quasi-two-dimensional slab, corresponding to the focal plane of a microscope, and show that the 3D nematic order parameter and its measurable projected analogue are very similar. We compare our results to confocal microscopy measurements on the orientation distribution function of systems of polarizable colloidal silica rods in an external electric field, demonstrating reasonably good agreement between theory and experiment without any free fit parameter.

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.

Orientation of a dielectric rod near a planar electrode.

We present experimental and theoretical results on suspensions of silica rods in DMSO-water, subjected to an applied electric field. The experimental results indicate that, if the electrode used for generating the electric field is in direct contact with the suspension, a fraction of the rods close to the electrode surface does not stand parallel to the field but instead lies flat on the electrode when the field is switched on. To explain these results theoretically, we modify the coupled dipole method to include "image dipoles", and find that a rod close to the electrode experiences not only the expected global potential energy minimum at an orientation parallel to the electric field, but also a local minimum several times the thermal energy in depth for orientations parallel to the electrode surface. Additionally, we indicate how the magnitude of the potential energy depends on the electric field strength and include results not only for negatively polarizable (which correspond to the aforementioned experimental system), but also for positively polarizable rods.

Effect of external electric fields on the phase behavior of colloidal silica rods.

We examine the effect of external electric fields on the behavior of colloidal silica rods. We find that the electric fields can be used to induce para-nematic and para-smectic phases, and to reduce the number of defects in smectic phases. At high field strengths, a new crystal structure was observed that consisted of strings of rods ordered in a hexagonal pattern in which neighboring rods were shifted along their length. We also present a simple model to describe this system, which we used in computer simulations to calculate the phase diagram for rods of L/D = 6, with L the end-to-end length of the rods and D the diameter of the rods. Our theoretical predictions for the phase behavior agree well with the experimental observations.

Dispersions of attractive semiflexible fiberlike colloidal particles from bacterial cellulose microfibrils.

We prepared dispersions from bacterial cellulose microfibrils (CMF) of a commercial Nata de Coco source. We used an ultra-high-energy mechanical deagglomeration process that is able to disperse the CMFs from the pellicle in which they are organized in an irregular network. Because of the strong attractions between the CMFs, the dispersion remained highly heterogeneous, consisting of fiber bundles, flocs, and voids spanning tens to hundreds of micrometers depending on concentration. The size of these flocs increased with CMF concentration, the size of the bundles stayed constant, and the size of the voids decreased. The observed percolation threshold in MFC dispersions is lower than the theoretical prediction, which is accounted for by the attractive interactions in the system. Because bacterial cellulose is chemically very pure, it can be used to study the interaction of attractive and highly shape-anisotropic, semiflexible fiberlike colloidal particles.

Synthesis of monodisperse, rodlike silica colloids with tunable aspect ratio.

Although the experimental study of spherical colloids has been extensive, similar studies on rodlike particles are rare because suitable model systems are scarcely available. To fulfill this need, we present the synthesis of monodisperse rodlike silica colloids with tunable dimensions. Rods were produced with diameters of 200 nm and greater and lengths up to 10 µm, resulting in aspect ratios from 1 to ∼25. The growth mechanism of these rods involves emulsion droplets inside which silica condensation takes place. Due to an anisotropic supply of reactants, the nucleus grows to one side only, resulting in rod formation. In concentrated dispersions, these rods self-assemble in liquid crystal phases, which can be studied quantitatively on the single particle level in three-dimensional real-space using confocal microscopy. Isotropic, paranematic, and smectic phases were observed for this system.