Assembly of cellulose nanocrystals in a levitating drop probed by time-resolved small angle X-ray scattering.

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.

Reinforcement Effects from Nanodiamond in Cellulose Nanofibril Films.

Although research on nanopaper structures from cellulose nanofibrils (CNFs) is well established, the mechanical behavior is not well understood, especially not when CNF is combined with hard nanoparticles. Cationic CNF (Q-CNF) was prepared and successfully decorated by anionic nanodiamond (ND) nanoparticles in hydrocolloidal form. The Q-CNF/ND nanocomposites were filtered from a hydrocolloid and dried. Unlike many other carbon nanocomposites, the Q-CNF/ND nanocomposites were optically transparent. Reinforcement effects from the nanodiamond were remarkable, such as Young's modulus (9.8 → 16.6 GPa) and tensile strength (209.5 → 277.5 MPa) at a content of only 1.9% v/v of ND, and the reinforcement mechanisms are discussed. Strong effects on CNF network deformation mechanisms were revealed by loading-unloading experiments. Scratch hardness also increased strongly with increased addition of ND.

Strong Surface Treatment Effects on Reinforcement Efficiency in Biocomposites Based on Cellulose Nanocrystals in Poly(vinyl acetate) Matrix.

In this work, the problem to disperse cellulose nanocrystals (CNC) in hydrophobic polymer matrices has been addressed through application of an environmentally friendly chemical modification approach inspired by clay chemistry. The objective is to compare the effects of unmodified CNC and modified CNC (modCNC) reinforcement, where degree of CNC dispersion is of interest. Hydrophobic functionalization made it possible to disperse wood-based modCNC in organic solvent and cast well-dispersed nanocomposite films of poly(vinyl acetate) (PVAc) with 1-20 wt % CNC. Composite films were studied by infrared spectroscopy (FT-IR), UV-vis spectroscopy, dynamic mechanical thermal analysis (DMTA), tensile testing, and field-emission scanning electron microscopy (FE-SEM). Strongly increased mechanical properties were observed for modCNC nanocomposites. The reinforcement efficiency was much lower in unmodified CNC composites, and specific mechanisms causing the differences are discussed.

Rod Packing in Chiral Nematic Cellulose Nanocrystal Dispersions Studied by Small-Angle X-ray Scattering and Laser Diffraction.

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.

Nanostructured membranes based on native chitin nanofibers prepared by mild process.

Procedures for chitin nanofiber or nanocrystal extraction from Crustaceans modify the chitin structure significantly, through surface deacetylation, surface oxidation and/or molar mass degradation. Here, very mild conditions were used to disintegrate chitin fibril bundles and isolate low protein content individualized chitin nanofibers, and prepare nanostructured high-strength chitin membranes. Most of the strongly 'bound' protein was removed. The degree of acetylation, crystal structure as well as length and width of the native chitin microfibrils in the organism were successfully preserved. Atomic force microscopy and scanning transmission electron microscopy, showed chitin nanofibers with width between 3 and 4 nm. Chitin membranes were prepared by filtration of hydrocolloidal nanofiber suspensions. Mechanical and optical properties were measured. The highest data so far reported for nanostructured chitin membranes was obtained for ultimate tensile strength, strain to failure and work to fracture. Strong correlation was observed between low residual protein content and high tensile properties and the reasons for this are discussed.

Highly conducting, strong nanocomposites based on nanocellulose-assisted aqueous dispersions of single-wall carbon nanotubes.

It is challenging to obtain high-quality dispersions of single-wall nanotubes (SWNTs) in composite matrix materials, in order to reach the full potential of mechanical and electronic properties. The most widely used matrix materials are polymers, and the route to achieving high quality dispersions of SWNT is mainly chemical functionalization of the SWNT. This leads to increased cost, a loss of strength and lower conductivity. In addition full potential of colloidal self-assembly cannot be fully exploited in a polymer matrix. This may limit the possibilities for assembly of highly ordered structural nanocomposites. Here we show that nanofibrillated cellulose (NFC) can act as an excellent aqueous dispersion agent for as-prepared SWNTs, making possible low-cost exfoliation and purification of SWNTs with dispersion limits exceeding 40 wt %. The NFC:SWNT dispersion may also offer a cheap and sustainable alternative for molecular self-assembly of advanced composites. We demonstrate semitransparent conductive films, aerogels and anisotropic microscale fibers with nanoscale composite structure. The NFC:SWNT nanopaper shows increased strength at 3 wt % SWNT, reaching a modulus of 13.3 GPa, and a strength of 307 MPa. The anisotropic microfiber composites have maximum conductivities above 200 S cm(-1) and current densities reaching 1400 A cm(-2).

Cellulose nanofiber orientation in nanopaper and nanocomposites by cold drawing.

To exploit the mechanical potential of native cellulose fibrils, we report on the preparation of nanopaper with preferred orientation of nanofibrillated cellulose (TEMPO-NFC) by cold drawing. The preparation route is papermaking-like and includes vacuum filtering of a TEMPO-oxidated NFC water dispersion, drawing in wet state and drying. The orientation of the fibrils in the nanopaper was assessed by AFM and wide-angle X-ray diffraction analysis, and the effect on mechanical properties of the resulting nanopaper structure was investigated by tensile tests. At high draw ratio, the degree of orientation is as high as 82 and 89% in-the-plane and cross-sectional planes of the nanopaper, respectively, and the Young's modulus is 33 GPa. This is much higher than mechanical properties of isotropic nanopaper. The cold drawing method can be also applied to NFC nanocomposites as demonstrated by preparation of TEMPO-NFC/hydroxyethyl cellulose (HEC) nanocomposites. The introduction of the soft HEC matrix allows further tailoring of the mechanical properties.

A transparent hybrid of nanocrystalline cellulose and amorphous calcium carbonate nanoparticles.

Nanocellulose hybrids are promising candidates for biodegradable multifunctional materials. Hybrids of nanocrystalline cellulose (NCC) and amorphous calcium carbonate (ACC) nanoparticles were obtained through a facile chemical approach over a wide range of compositions. Controlling the interactions between NCC and ACC results in hard, transparent structures with tunable composition, homogeneity and anisotropy.

Determination of Young's modulus for nanofibrillated cellulose multilayer thin films using buckling mechanics.

The Young's modulus of multilayer films containing nanofibrillated cellulose (NFC) and polyethyleneimine (PEI) was determined using the strain-induced elastic buckling instability for mechanical measurements (SIEBIMM) technique. (1) Multilayer films were built up on polydimethylsiloxane substrates using electrostatic layer-by-layer assembly. At 50% relative humidity, SIEBIMM gave a constant Young's modulus of 1.5 ± 0.2 GPa for 35-75 nm thick films. Conversely, in vacuum, the Young's modulus was 10 times larger, at 17.2 ± 1.2 GPa. A slight decrease in buckling wavelength with increasing strain was observed by scanning electron microscopy with in situ compression, and above 10% strain, extensive cracking parallel to the compressive direction occurred. We conclude that whereas PEI acts as a "glue" to hold multiple layers of NFC together, it prevents full development of hydrogen bonding and specific fibril-fibril interactions, and at high humidity, its hygroscopic nature decreases the elastic modulus when compared with pure NFC films.