Cellulose nanocrystals (CNCs), ribbonlike crystalline nanoparticles, are a biobased material that can be a great alternative to obtaining films with tunable optical properties. Iridescent and light-diffracting films can be readily obtained via the drying of a suspension of these cellulose nanocrystals. The characteristics of the particle deposition process together with the self-assembly in the precluding suspension has a direct effect on the optical properties of the obtained films. Particle deposition onto a substrate is affected by the flow dynamics inside sessile droplets and usually yields a ring-shaped deposition pattern commonly referred to as the coffee-ring effect. We set out to measure and describe the drying kinetics under different conditions. We found that the Marangoni flow inside the droplet was too small to counteract the capillary flow that deposits CNCs at the edges, resulting in the coffee-ring effect, irrespective of the atmospheric humidity. By varying the amount of ethanol in the atmosphere, we were able to find a balance between (1) colloidal stability in the droplet, which is reduced by ethanol diffusion into the droplet, and (2) increasing Marangoni flow relative to capillary flow inside the droplet by changing the droplet surface tension. We could thus make iridescent films with a uniform thickness.

In this paper, we use dynamic light scattering in polarized and depolarized modes to determine the translational and rotational diffusion coefficients of concentrated rodlike cellulose nanocrystals in aqueous suspension. Within the range of studied concentrations (1–5 wt %), the suspension starts a phase transition from an isotropic to an anisotropic state as shown by polarized light microscopy and viscosity measurements. Small-angle neutron scattering measurements also confirmed the start of cellulose nanocrystal alignment and a decreasing distance between the cellulose nanocrystals with increasing concentration. As expected, rotational and translational diffusion coefficients generally decreased with increasing concentration. However, the translational parallel diffusion coefficient was found to show a local maximum at the onset of the isotropic-to-nematic phase transition. This is attributed to the increased available space for rods to move along their longitudinal axis upon alignment. This increased parallel diffusion coefficient thus confirms the general idea that rodlike particles gain translational entropy upon alignment while paying the price for losing rotational degrees of freedom. Once the concentration increases further, diffusion becomes more hindered even in the aligned regions due to a reduction in the rod separation distance. This leads once again to a decrease in translational diffusion coefficients. Furthermore, the relaxation rate for fast mode translational diffusion (parallel to the long particle axis) exhibited two regimes of relaxation behavior at concentrations where significant alignment of the rods is measured. We attribute this unusual dispersive behavior to two length scales: one linked to the particle length (at large wavevector q) and the other to a twist fluctuation correlation length (at low wavevector q) along the cellulose nanocrystal rods that is of a larger length when compared to the actual length of rods and could be linked to the size of aligned domains.

The thermodynamics of interactions between cations of the second group of the periodic table and differently negatively charged cellulose nanocrystals was investigated using isothermal titration calorimetry (ITC). The interaction of cations with the negatively charged CNCs was found to be endothermic and driven by an increase in entropy upon adsorption of the ions, due to an increase in degrees of freedom gained by the surface bound water upon ion adsorption. The effect was pH-dependent, showing an increase in enthalpy for cellulose suspensions at near-neutral pH (6.5) when compared to acidic pH (2). Sulfated cellulose nanoparticles were found to readily interact with divalent ions at both pH levels. The adsorption on carboxylate nanocrystals was found to be pH dependent, showing that the carboxylic group needs to be in the deprotonated form to interact with divalent ions. For the combined system (sulfate and carboxylate present at the same time), at neutral pH, the adsorption enthalpy was higher than the value obtained from cellulose nanocrystals containing a single functional group, while the association constant was higher due to an increased favorable entropic contribution. The higher entropic contribution indicates a more restricted surface-bound water layer when multiple functionalities are present. The stoichiometric number n was nearly constant for all systems, showing that the adsorption depends almost completely on the ion valency and on the amount of ionic groups on the CNC surface, independent of the type of functional group on the CNC surface as long as it is deprotonated. In addition, we showed that the reduction in Gibbs free energy drives the ionotropic gelation of nanocellulose suspensions, and we show that ITC is able to detect gel formation at the same time as determining the critical association concentration.

Sulfuric acid hydrolysis of native cellulose fibers results in colloidally stable suspensions of cellulose nanocrystals (CNCs). We have investigated the effect of the cellulose source on the suspension properties of CNCs extracted from cotton and wood sources using a comparable preparation strategy. The structural properties were revealed to be similar within the given standard deviation and prevalent polydispersity, whereas other properties such as liquid crystalline phase behavior, viscosity, diffusion coefficients, and surface tension were found to differ significantly. This study shows that ostensibly similar suspensions may exhibit rather differing behaviors and attempts to interpret this phenomenon. This finding shows that full characterization and a detailed description of the preparation of the nanocrystals used in publications are extremely important and should be reported in detail in all instances.