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.

Random three-dimensional jammed packings of elastic shells acting as force sensors.

In a jammed solid of granular particles, the applied stress is in-homogeneously distributed within the packing. A full experimental characterization requires measurement of all the interparticle forces, but so far such measurements are limited to a few systems in two and even fewer in three dimensions. Particles with the topology of (elastic) shells are good local force sensors as relatively large deformations of the shells result from relatively small forces. We recently introduced such fluorescent shells as a model granular system in which force distributions can be determined in three dimensions using confocal microscopy and quantitative image analysis. An interesting aspect about these shells that differentiates them from other soft deformable particles is their buckling behavior at higher compression. This leads to deformations that do not conserve the inner volume of the particle. Here we use this system to accurately measure the contact forces in a three-dimensional packing of shells subjected to a static anisotropic compression and to shear. At small deformations forces are linear, however, for a buckled contact, the restoring force is related to the amount of deformation by a square root law, as follows from the theory of elasticity of shells. Near the unjamming-jamming transition (point J), we found the probability distribution of the interparticle forces P(f) to decay nearly exponentially at large forces, with little evidence of long-range force chains in the packings. As the packing density is increased, the tail of the distribution was found to crossover to a Gaussian, in line with other experimental and simulation studies. Under a small shear strain, up to 0.216, applied at an extremely low shear rate, we observed a shear-induced anisotropy in both the pair correlation function and contact force network; however, no appreciable change was seen in the number of contacts per particle.

Jammed elastic shells - a 3D experimental soft frictionless granular system.

We present a new experimental system of monodisperse, soft, frictionless, fluorescent labeled elastic shells for the characterization of structure, universal scaling laws and force networks in 3D jammed matter. The elastic shells in a jammed packing are deformed in such a way that at each contact one of the shells buckles with a dimple and the other remain spherical, closely resembling overlapping spheres. Using confocal microscopy, we obtained 3D stacks of images of shells at different volume fractions which were subsequently processed in ImageJ software to find their coordinates. The determination of 3D coordinates involved three steps: locating the edges of shells in all 2D slices, analyzing their shape and subsequently finding their 2D coordinates, and finally determining their 3D centers by grouping the corresponding 2D coordinates. From this analysis routine we obtained particle coordinates with sub-pixel accuracy. In a contact pair we also identified the shell that underwent buckling forming a dimple by analyzing the intensity profile of a line that connects the centers of particle pairs. The amorphous structure of the packing was analyzed as a function of distance to the jamming threshold by investigating the radial distribution function, bond order parameters, contact numbers and the number of dimples per particle (buckling number), which is a unique property of this system. We find that the power law scaling of the contact number with excess volume fraction deviated from theoretical and computer simulation predictions. In addition, the buckling number also showed a similar scaling as that of the contact number with distance to the jamming transition.

Unloading and reloading colloidal microcapsules with apolar solutions by controlled and reversible buckling.

We introduce a new experimental method to encapsulate and release oils and fluorescent molecules into preformed elastic colloidal microcapsules of polydimethylsiloxane (PDMS)-filled siloxane shells, which are cross-linked with tetraethoxysilane. The method uses controlled buckling, where the volume of the capsule is reduced by dissolving the PDMS oil inside the capsule by surfactant micelles. This results in a change in the morphology of the capsule that depends on the ratio of shell thickness to total particle radius (d/Rt). Microcapsules of d/Rt in the range 0.007-0.05 formed microbowls upon decreasing the inner volume. The amount of oil released or dissolved by the micelles can be directly related to the concentration of surfactant. By tuning the amount of oil released, we can make microbowls of variable depth. In addition, we demonstrate that the microbowls can be further used to load different oils like silicone oil, hydrocarbons, and apolar dyes. The elasticity of the capsule wall and the leftover PDMS oil inside the capsule provide the principal driving forces by which one can promote the uptake of different oils, including dissolved dye molecules.