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Self-assembly of cellulose nanocrystals (CNCs) doped with anisotropic gold nanorods (AuNRs) was studied by small-angle neutron scattering. Correlation distances and structured domains were analysed to determine the influence of CNC and AuNR concentration on structuring. The transfer of the nematic structure of CNCs to AuNRs is explained in terms of an entropy-driven evolution from an isotropic to a cholesteric phase, with small nematic domains already present in the "isotropic" phase in equilibrium with the chiral nematic phase.

The lyotropic cholesteric liquid crystal phase developed by suspensions of cellulose nanocrystals (CNCs) has come increasingly into focus from numerous directions over the last few years. In part, this is because CNC suspensions are sustainably produced aqueous suspensions of a fully bio-derived nanomaterial with attractive properties. Equally important is the interesting and useful behavior exhibited by solid CNC films, created by drying a cholesteric-forming suspension. However, the pathway along which these films are realized, starting from a CNC suspension that may have low enough concentration to be fully isotropic, is more complex than often appreciated, leading to reproducibility problems and confusion. Addressing a broad audience of physicists, chemists, materials scientists and engineers, this Review focuses primarily on the physics and physical chemistry of CNC suspensions and the process of drying them. The ambition is to explain rather than to repeat, hence we spend more time than usual on the meanings and relevance of the key colloid and liquid crystal science concepts that must be mastered in order to understand the behavior of CNC suspensions, and we present some interesting analyses, arguments and data for the first time. We go through the development of cholesteric nuclei (tactoids) from the isotropic phase and their potential impact on the final dry films; the spontaneous CNC fractionation that takes place in the phase coexistence window; the kinetic arrest that sets in when the CNC mass fraction reaches ~10 wt.\%, preserving the cholesteric helical order until the film has dried; the 'coffee-ring effect' active prior to kinetic arrest, often ruining the uniformity in the produced films; and the compression of the helix during the final water evaporation, giving rise to visible structural color in the films.

The ability to probe the assembly, gelation, and helicoidal nsolidation of cellulose nanocrystal (CNC) dispersions at high ncentrations can provide unique insight into the assembly and can sist optimized manufacturing of CNC-based photonic and structural terials. In this Feature Article, we review and discuss the ncentration dependence of the structural features, characterized by e particle separation distance and the helical pitch, at CNC ncentrations (c) that range from the isotropic state, over the phasic range, to the fully liquid crystalline state. The structure olution of CNC dispersions probed by time resolved small-angle X-ray attering during evaporation-induced assembly highlighted the portance of gelation and consolidation at high concentrations. We iefly discuss how the homogeneity of helicoidal nanostructures in dry, QC 20190502

Inspired by the Bogolanfini dyeing technique, we report how flexible nanofibrillated cellulose (CNF) films can be functionalized and patterned by surface-bound nanoparticles of hydrolyzable tannins and multivalent metal ions with tunable colors. Molecular dynamics simulations show that gallic acid (GA) and ellagic acid (EA) rapidly adsorb and assemble on the CNF surface, and atomic force microscopy confirms that nanosized GA assemblies cover the surface of the CNF. CNF films were patterned with tannin-metal ion nanoparticles by an in-fibre reaction between the pre-impregnated tannin and the metal ions in the printing ink. Spectroscopic studies show that the Fe-III/II ions interact with GA and form surface-bound, stable GA-Fe-III/II nanoparticles. The functionalization and patterning of CNF films with metal ion-hydrolyzable tannin nanoparticles is a versatile route to functionalize films based on renewable materials and of interest for biomedical and environmental applications.

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 t

The formation of nematically-ordered cellulose nanofiber (CNF) suspensions with an order parameter f(max) approximate to 0.8 is studied by polarized optical microscopy, small-angle X-ray scattering (SAXS), and rheological measurements as a function of CNF concentration. The wide range of CNF concentrations, from 0.5 wt% to 4.9 wt%, is obtained using osmotic dehydration. The rheological measurements show a strong entangled network over all the concentration range whereas SAXS measurements indicate that at concentrations >1.05 wt% the CNF suspension crosses an isotropic-anisotropic transition that is accompanied by a dramatic increase of the optical birefringence. The resulting nanostructures are modelled as mass fractal structures that converge into co-existing nematically-ordered regions and network-like regions where the correlation distances decrease with concentration. The use of rapid, upscalable osmotic dehydration is an effective method to increase the concentration of CNF suspensions while partly circumventing the gel/glass formation. The facile formation of highly ordered fibers can result in materials with interesting macroscopic properties.

We have followed the structural evolution during evaporation-induced self-assembly of sulfonated cellulose nanocrystal (CNC) in the presence of H+ and Li+ counterions by small-angle X-ray scattering. Drying of CNC-H dispersions results in ordered films that could not be readily redispersed, while the CNC-Li films were disordered and prone to reswelling and redispersion. The scaling of the separation distance (d) between CNC particles and the particle concentration (c) shows that the CNC-H dispersions display a unidimensional contraction of the nematic structure (d alpha c(-1)) during drying, while the CNC-Li dispersions consolidate isotropically (d alpha c(-1/3)), which is characteristic for hydrogels with no preferential orientation. Temporal evolution of the structure factor and complementary dynamic light-scattering measurements show that CNC-Li is more aggregated than CNC-H during evaporation-induced assembly. Insights on the structural evolution during CNC assembly and redispersion can promote development of novel and optimized processing routes of nanocellulose-based materials.

Assembly of bio-based nano-sized particles into complex architectures and morphologies is an area of fundamental interest and technical importance. We have investigated the assembly of sulfonated cellulose nanocrystals (CNC) dispersed in a shrinking levitating aqueous drop using time-resolved small angle X-ray scattering (SAXS). Analysis of the scaling of the particle separation distance (d) with particle concentration (c) was used to follow the transition of CNC dispersions from an isotropic state at 1-2 vol% to a compressed nematic state at particle concentrations above 30 vol%. Comparison with SAXS measurements on CNC dispersions at near equilibrium conditions shows that evaporation-induced assembly of CNC in large levitating drops is comparable to bulk systems. Colloidal states with d vs. c scalings intermediate between isotropic dispersions and unidirectional compression of the nematic structure could be related to the biphasic region and gelation of CNC. Nanoscale structural information of CNC assembly up to very high particle concentrations can help to fabricate nanocellulose-based materials by evaporative methods.

Colloids of electrically charged nanorods can spontaneously develop a fluid yet ordered liquid crystal phase, but this ordering competes with a tendency to form a gel of percolating rods. The threshold for ordering is reduced by increasing the rod aspect ratio, but the percolation threshold is also reduced with this change; hence, prediction of the outcome is nontrivial. Here, we show that by establishing the phase behavior of suspensions of cellulose nanocrystals(CNCs) fractionated according to length, an increased aspect ratio can strongly favor liquid crystallinity without necessarily influencing gelation. Gelation is instead triggered by increasing the counterion concentration until theCNCs lose colloidal stability, triggering linear aggregation, which promotes percolation regardless of the original rod aspect ratio. Our results shine new light on the competition between liquid crystal formation and gelation in nanoparticle suspensions and provide a path for enhanced control of CNC self-organization for applications in photonic crystal paper or advanced composites.

We investigate the effect of shear flow applied during the drying of aqueous suspension of cellulose nanocrystals on optical reflective properties and structural characteristics of the resulting solidified films. Shear flow can significantly improve internal structural homogeneity of the films, while its effect on optical reflective properties is relatively minor. The measured width of the selective reflection peak is an order of magnitude larger than expected for an ideal helically modulated structure, which reflects a distribution of pitch values and possibly also of regimes of distorted helical modulation. We attribute these imperfections to the broad size distribution of the cellulose nanocrystals.

We investigate the effect of shear flow applied during the drying of aqueous suspension of cellulose nanocrystals on optical reflective properties and structural characteristics of the resulting solidified films. Shear flow can significantly improve internal structural homogeneity of the films, while its effect on optical reflective properties is relatively minor. The measured width of the selective reflection peak is an order of magnitude larger than expected for an ideal helically modulated structure, which reflects a distribution of pitch values and possibly also of regimes of distorted helical modulation. We attribute these imperfections to the broad size distribution of the cellulose nanocrystals.

The packing of cellulose nanocrystals (CNC) in the anisotropic chiral nematic phase has been investigated over a wide concentration range by small angle X-ray scattering (SAXS) and laser diffraction. The average separation distance between the CNCs and the average pitch of the chiral nematic phase have been determined over the entire isotropic-anisotropic biphasic region. The average separation distances range from 51 nm, at the onset of the anisotropic phase formation, to 25 nm above 6 vol% (fully liquid crystalline phase) whereas the average pitch varies from 15.5 μm down to ≈2 μm as φ increases from 2.5 up to 6.5 vol%. Using the cholesteric order, we determine that the twist angle between neighboring CNCs increases from about 1 ° up to 4 ° as φ increases from 2.5 up to 6.5 vol%. The dependence of the twisting on the volume fraction was related to the increase in the magnitude of the repulsive interactions between the charged rods as the average separation distance decrease.

We have studied how cellulose nanocrystals (CNC) self-assemble into liquid crystalline phases in shrinking, isolated droplets. By adjusting the water dissolution rate of an aqueous CNC droplet immersed in a binary toluene-ethanol mixture we can control the final morphology of the consolidated microbead. At low ethanol concentration in the surrounding fluid dense microbeads of spherical morphology are produced while collapsed core-shell particles are obtained at high ethanol concentration. Polarized light microscopy was used to follow the spatial evolution and coalescence of birefringent spheroids during droplet shrinkage. Electron microscopy reveals the resultant nematic microstructure. This method of confined CNC assembly provides thus the possibility to prepare ordered microbeads, which can be useful as templates or for their optical properties., QC 20150720

The packing of cellulose nanocrystals (CNC) in the anisotropic chiral nematic phase has been investigated over a wide concentration range by small-angle X-ray scattering (SAXS) and laser diffraction. The average separation distance between the CNCs and the average pitch of the chiral nematic phase have been determined over the entire isotropic-anisotropic biphasic region. The average separation distances range from 51 nm, at the onset of the anisotropic phase formation, to 25 nm above 6 vol % (fully liquid crystalline phase) whereas the average pitch varies from approximate to 15 mu m down to approximate to 2 mu m as phi increases from 2.5 up to 6.5 vol %. Using the cholesteric order, we determine that the twist angle between neighboring CNCs increases from about 1 degrees up to 4 degrees as phi increases from 2.5 up to 6.5 vol %. The dependence of the twisting on the volume fraction was related to the increase in the magnitude of the repulsive interactions between the charged rods as the average separation distance decreases., QC 20150720

The increasing need to replace fossil fuels as a source of energy and raw material is resulting in extensive research efforts towards identifying and developing high performance materials and devices based on renewable sources. Cellulose being the most versatile and abundant biopolymer in nature is one of the obvious choices. Cellulose, due to its properties that arise from the hierarchical structure, has been used for millennia by mankind although it is currently used, in the form of microfibers, mainly in the paper and pulp industry. However, many efforts are being directed towards retrieving even smaller cellulose constituents such as nanofibers and nanocrystals (i.e., nanocellulose), which can actually be used in high performance materials. In order to do so, a better understanding of the behavior and interactions between these novel nanomaterials are required. Moreover, the combination of nanocellulose with inorganic nanoparticles bears a great potential that can open the door to multifunctional materials based on a renewable component. In this work, the anisotropic behavior, i.e., the formation of a chiral nematic phase, of cellulose nanocrystals (CNC) initially dispersed in aqueous media spanning a wide volume fraction range has been studied by small angle X-ray scattering (SAXS) and laser diffraction. The analysis shows that the twist angle between neighboring CNCs increased from ~1° up to ~4° as the CNC volume fraction increased from 2.5 to 6.5 vol%. Also, the drying of an aqueous CNC droplet immersed in a binary toluene/ethanol mixture was studied and monitored in-situ by polarized video microscopy, where the influence of the water dissolution rate on the morphology of the resulting microbeads was investigated by scanning electron microscopy. The morphology of the microbeads depends not only on the drying speed but also on the initial starting CNC volume fraction. In this regard, the influence of the degrees of liquid crystallinity on the formation of a ch, At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: Submitted. Paper 2: Submitted. Paper 4: Manuscript.

Nanocellulose fibrils are ubiquitous in nature and nanotechnologies but their mesoscopic structural assembly is not yet fully understood. Here we study the structural features of rod-like cellulose nanoparticles on a single particle level, by applying statistical polymer physics concepts on electron and atomic force microscopy images, and we assess their physical properties via quantitative nanomechanical mapping. We show evidence of right-handed chirality, observed on both bundles and on single fibrils. Statistical analysis of contours from microscopy images shows a non-Gaussian kink angle distribution. This is inconsistent with a structure consisting of alternating amorphous and crystalline domains along the contour and supports process-induced kink formation. The intrinsic mechanical properties of nanocellulose are extracted from nanoindentation and persistence length method for transversal and longitudinal directions, respectively. The structural analysis is pushed to the level of single cellulose polymer chains, and their smallest associated unit with a proposed 2 x 2 chain-packing arrangement.

Carbon aerogels with large open pores and high surface area are fabricated via pyrolysis of a readily available natural resource, e. g., bacterial nanocellulose (BNC) aerogels. Freeze-drying of the BNC hydrogels is used to preserve the 3D open network structure upon calcination whereas using Fe(III) improves the yield and H/C ratio. These carbon aerogels are explored as anodes in lithium ion batteries where it is shown that they deliver superior capacity retention and rate performance compared to other carbon-based materials., QC 20140603

Cellulose nanocrystals (CNCs), produced by the acid hydrolysis of wood, cotton or other cellulose-rich sources, constitute a renewable nanosized raw material with a broad range of envisaged uses: for example, in composites, cosmetics and medical devices. The intriguing ability of CNCs to self-organize into a chiral nematic (cholesteric) liquid crystal phase with a helical arrangement has attracted significant interest, resulting in much research effort, as this arrangement gives dried CNC films a photonic band gap. The films thus acquire attractive optical properties, creating possibilities for use in applications such as security papers and mirrorless lasing. In this critical review, we discuss the sensitive balance between glass formation and liquid crystal self-assembly that governs the formation of the desired helical structure. We show that several as yet unclarified observations-some constituting severe obstacles for applications of CNCs-may result from competition between the two phenomena. Moreover, by comparison with the corresponding self-assembly processes of other rod-like nanoparticles, for example, carbon nanotubes and fd virus particles, we outline how further liquid crystal ordering phenomena may be expected from CNCs if the suspension parameters can be better controlled. Alternative interpretations of some unexpected phenomena are provided, and topics for future research are identified, as are new potential application strategies., AuthorCount:7

Cellulose nanocrystals (CNCs), produced by the acid hydrolysis of wood, cotton or other cellulose-rich sources, constitute a renewable nanosized raw material with a broad range of envisaged uses: for example, in composites, cosmetics and medical devices. The intriguing ability of CNCs to self-organize into a chiral nematic (cholesteric) liquid crystal phase with a helical arrangement has attracted significant interest, resulting in much research effort, as this arrangement gives dried CNC films a photonic band gap. The films thus acquire attractive optical properties, creating possibilities for use in applications such as security papers and mirrorless lasing. In this critical review, we discuss the sensitive balance between glass formation and liquid crystal self-assembly that governs the formation of the desired helical structure. We show that several as yet unclarified observations—some constituting severe obstacles for applications of CNCs—may result from competition between the two phenomena. Moreover, by comparison with the corresponding self-assembly processes of other rod-like nanoparticles, for example, carbon nanotubes and fd virus particles, we outline how further liquid crystal ordering phenomena may be expected from CNCs if the suspension parameters can be better controlled. Alternative interpretations of some unexpected phenomena are provided, and topics for future research are identified, as are new potential application strategies.