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. NPG Asia Materials (2014) 6, e80; doi:10.1038/am.2013.69; published online 10 January 2014Keywords: cholesteric; gel; glass; liquid crystal; nanocellulose; photonic crystal; self-assembly INTRODUCTION Nanomaterials based on renewable resources are attracting rapidly growing interest, both from a fundamental scientific point of view and from the perspective of developing novel structural and functional macroscopic materials. 1,2 Using nature-based nanomaterials offers ecological advantages, and the extraordinary mechanical performance and/or photonic crystal character of biological composites such as bone, nacre, wood, beetle scales and butterfly wings is also an important inspiration for the development of new multifunctional materials. [3][4][5] However, full utilization of the intrinsic properties of nanosized starting materials requires the development of robust and versatile synthetic and processing routes to control assembly over several length scales. [6][7][8] Cellulose, one of the most versatile and widely found biopolymers in nature, has been used by humans for millennia as a building material, an energy source, a component of clothing and for storing and sharing knowledge and culture. Today, cellulose materials are used in a wide range of applications, and the paper and pulp industry
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 × 2 chain-packing arrangement.
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 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 decreases.
The intrinsic ability of cellulose nanocrystals (CNCs) to self-organize into films and bulk materials with helical order in a cholesteric liquid crystal is scientifically intriguing and potentially important for the production of renewable multifunctional materials with attractive optical properties. A major obstacle, however, has been the lack of control of helix direction, which results in a defect-rich, mosaic-like domain structure. Herein, a method for guiding the helix during film formation is introduced, which yields dramatically improved uniformity, as confirmed by using polarizing optical and scanning electron microscopy. By raising the CNC concentration in the initial suspension to the fully liquid crystalline range, a vertical helix orientation is promoted, as directed by the macroscopic phase boundaries. Further control of the helix orientation is achieved by subjecting the suspension to a circular shear flow during drying.
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 the CNCs 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.
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.
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.
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.
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