Cellulose fibrils with widths in the nanometer range are nature-based materials with unique and potentially useful features. Most importantly, these novel nanocelluloses open up the strongly expanding fields of sustainable materials and nanocomposites, as well as medical and life-science devices, to the natural polymer cellulose. The nanodimensions of the structural elements result in a high surface area and hence the powerful interaction of these celluloses with surrounding species, such as water, organic and polymeric compounds, nanoparticles, and living cells. This Review assembles the current knowledge on the isolation of microfibrillated cellulose from wood and its application in nanocomposites; the preparation of nanocrystalline cellulose and its use as a reinforcing agent; and the biofabrication of bacterial nanocellulose, as well as its evaluation as a biomaterial for medical implants.

Toward exploiting the attractive mechanical properties of cellulose I nanoelements, a novel route is demonstrated, which combines enzymatic hydrolysis and mechanical shearing. Previously, an aggressive acid hydrolysis and sonication of cellulose I containing fibers was shown to lead to a network of weakly hydrogen-bonded rodlike cellulose elements typically with a low aspect ratio. On the other hand, high mechanical shearing resulted in longer and entangled nanoscale cellulose elements leading to stronger networks and gels. Nevertheless, a widespread use of the latter concept has been hindered because of lack of feasible methods of preparation, suggesting a combination of mild hydrolysis and shearing to disintegrate cellulose I containing fibers into high aspect ratio cellulose I nanoscale elements. In this work, mild enzymatic hydrolysis has been introduced and combined with mechanical shearing and a high-pressure homogenization, leading to a controlled fibrillation down to nanoscale and a network of long and highly entangled cellulose I elements. The resulting strong aqueous gels exhibit more than 5 orders of magnitude tunable storage modulus G' upon changing the concentration. Cryotransmission electron microscopy, atomic force microscopy, and cross-polarization/magic-angle spinning (CP/MAS) 13C NMR suggest that the cellulose I structural elements obtained are dominated by two fractions, one with lateral dimension of 5-6 nm and one with lateral dimensions of about 10-20 nm. The thicker diameter regions may act as the junction zones for the networks. The resulting material will herein be referred to as MFC (microfibrillated cellulose). Dynamical rheology showed that the aqueous suspensions behaved as gels in the whole investigated concentration range 0.125-5.9% w/w, G' ranging from 1.5 Pa to 105 Pa. The maximum G' was high, about 2 orders of magnitude larger than typically observed for the corresponding nonentangled low aspect ratio cellulose I gels, and G' scales with concentration with the power of approximately three. The described preparation method of MFC allows control over the final properties that opens novel applications in materials science, for example, as reinforcement in composites and as templates for surface modification.

A new type of nanocellulosic material has been prepared by high-pressure homogenization of carboxymethylated cellulose fibers followed by ultrasonication and centrifugation. This material had a cylindrical cross-section as shown by transmission electron microscopy with a diameter of 5-15 nm and a length of up to 1 microm. Calculations, using the Poisson-Boltzmann equation, showed that the surface potential was between 200 and 250 mV, depending on the pH, the salt concentration, and the size of the fibrils. They also showed that the carboxyl groups on the surface of the nanofibrils are not fully dissociated until the pH has reached pH = approximately 10 in deionized water. Calculations of the interaction between the fibrils using the Derjaguin-Landau-Verwey-Overbeek theory and assuming a cylindrical geometry indicated that there is a large electrostatic repulsion between these fibrils, provided the carboxyl groups are dissociated. If the pH is too low and/or the salt concentration is too high, there will be a large attraction between the fibrils, leading to a rapid aggregation of the fibrils. It is also possible to form polyelectrolyte multilayers (PEMs) by combining different types of polyelectrolytes and microfibrillated cellulose (MFC). In this study, silicon oxide surfaces were first treated with cationic polyelectrolytes before the surfaces were exposed to MFC. The build-up of the layers was monitored with ellipsometry, and they show that it is possible to form very well-defined layers by combinations of MFC and different types of polyelectrolytes and different ionic strengths of the solutions during the adsorption of the polyelectrolyte. A polyelectrolyte with a three-dimensional structure leads to the build-up of thick layers of MFC, whereas the use of a highly charged linear polyelectrolyte leads to the formation of thinner layers of MFC. An increase in the salt concentration during the adsorption of the polyelectrolyte results in the formation of thicker layers of MFC, indicating that the structure of the adsorbed polyelectrolyte has a large influence on the formation of the MFC layer. The films of polyelectrolytes and MFC were so smooth and well-defined that they showed clearly different interference colors, depending on the film thickness. A comparison between the thickness of the films, as measured with ellipsometry, and the thickness estimated from their colors showed good agreement, assuming that the films consisted mainly of solid cellulose with a refractive index of 1.53. Carboxymethylated MFC is thus a new type of nanomaterial that can be combined with oppositely charged polyelectrolytes to form well-defined layers that may be used to form, for example, new types of sensor materials.

Recently it was shown that enzymatic and mechanical processing of macroscopic cellulose fibers lead to disintegration of long and entangled native cellulose I nanofibers in order to form mechanically strong aqueous gels (Pa ¨a ¨kko ¨et al., Biomacromolecules, 2007Biomacromolecules, , 8, 1934. Here we demonstrate that (1) such aqueous nanofibrillar gels are unexpectedly robust to allow formation of highly porous aerogels by direct water removal by freeze-drying, (2) they are flexible, unlike most aerogels that suffer from brittleness, and (3) they allow flexible hierarchically porous templates for functionalities, e.g. for electrical conductivity. No crosslinking, solvent exchange nor supercritical drying are required to suppress the collapse during the aerogel preparation, unlike in typical aerogel preparations. The aerogels show a high porosity of $98% and a very low density of ca. 0.02 g cm À3 . The flexibility of the aerogels manifests as a particularly high compressive strain of ca. 70%. In addition, the structure of the aerogels can be tuned from nanofibrillar to sheet-like skeletons with hierarchical micro-and nanoscale morphology and porosity by modifying the freeze-drying conditions. The porous flexible aerogel scaffold opens new possibilities for templating organic and inorganic matter for various functionalities. This is demonstrated here by dipping the aerogels in an electrically conducting polyaniline-surfactant solution which after rinsing off the unbound conducting polymer and drying leads to electrically conducting flexible aerogels with relatively high conductivity of around 1 Â 10 À2 S cm À1 . More generally, we foresee a wide variety of functional applications for highly porous flexible biomatter aerogels, such as for selective delivery/separation, tissue-engineering, nanocomposites upon impregnation by polymers, and other medical and pharmaceutical applications.

Chemical vapor deposition of a thin titanium dioxide (TiO 2 ) fi lm on lightweight native nanocellulose aerogels offers a novel type of functional material that shows photoswitching between water-superabsorbent and water-repellent states. Cellulose nanofi brils (diameters in the range of 5-20 nm) with native crystalline internal structures are topical due to their attractive mechanical properties, and they have become relevant for applications due to the recent progress in the methods of their preparation. Highly porous, nanocellulose aerogels are here fi rst formed by freeze-drying from the corresponding aqueous gels. Well-defi ned, nearly conformal TiO 2 coatings with thicknesses of about 7 nm are prepared by chemical vapor deposition on the aerogel skeleton. Weighing shows that such TiO 2 -coated aerogel specimens essentially do not absorb water upon immersion, which is also evidenced by a high contact angle for water of 140 ° on the surface. Upon UV illumination, they absorb water 16 times their own weight and show a vanishing contact angle on the surface, allowing them to be denoted as superabsorbents. Recovery of the original absorption and wetting properties occurs upon storage in the dark. That the cellulose nanofi brils spontaneously aggregate into porous sheets of different length scales during freeze-drying is relevant: in the water-repellent state they may stabilize air pockets, as evidenced by a high contact angle, in the superabsorbent state they facilitate rapid water-spreading into the aerogel cavities by capillary effects. The TiO 2 -coated nanocellulose aerogels also show photooxidative decomposition, i.e., photocatalytic activity, which, in combination with the porous structure, is interesting for applications such as water purifi cation. It is expected that the present dynamic, externally controlled, organic/inorganic aerogels will open technically relevant approaches for various applications.

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This paper deals, with cationically modified NanoFibrillar Cellulose (cat NFC), obtained by reacting a dissolving pulp with 2,3-epoxypropyl trimethylammonium chloride (EPTMAC). The cat NFC was thoroughly characterized in terms of morphology and physical properties. The dimensions of individual cellulose nanofibrils were determined by atomic force microscopy (AFM) imaging in water and in air. Fibrils as thin as 0.8-1.2 nm were observed in water. The fibril diameter changed upon drying and the average size was further quantified by image analysis. The experiments showed the importance of characterizing nanocellulosic materials in situ before drying. The fibril size in air was confirmed by cryogenic transmission electron microscopy (cryo-TEM), and it was found to be 2.6-3.0 nm. Smooth ultrathin films of cationic NFC were prepared by spincoating on silica substrates. The effect of electrolyte concentration and pH on swelling of the cationic NFC film was studied using a quartz crystal microbalance with dissipation. The results showed that at pH = 8 the cat NFC film was insensitive to electrolyte changes while at pH = 4.5, the water content of the film decreased with increasing ionic strength. The electrophoretic mobility measurements showed a cationic zeta potential for the cat NFC that decreased at increasing pH, verifying the swelling behaviour.

We produced microfibrillated cellulose by passing carboxymethylated sulfite-softwood-dissolving pulp with a relatively low hemicellulose content (4.5%) through a high-shear homogenizer. The resulting gel was subjected to as many as three additional homogenization steps and then used to prepare solvent-cast films. The optical, mechanical, and oxygen-barrier properties of these films were determined. A reduction in the quantity and appearance of large fiber fragments and fiber aggregates in the films as a function of increasing homogenization was illustrated with optical microscopy, atomic force microscopy, and scanning electron microscopy. Film opacity decreased with increasing homogenization, and the use of three additional homogenization steps after initial gel production resulted in highly transparent films. The oxygen permeability of the films was not significantly influenced by the degree of homogenization, whereas the mean tensile strength, modulus of elasticity, and strain at break were increased by two or three extra homogenization steps.