Shuji Fujisawa

Ultrastrong and high gas-barrier nanocellulose/clay-layered composites.

Nanocellulose/montmorillonite (MTM) composite films were prepared from 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized cellulose nanofibrils (TOCNs) with an aspect ratio of >200 dispersed in water with MTM nanoplatelets. The composite films were transparent and flexible and showed ultrahigh mechanical and oxygen barrier properties through the nanolayered structures, which were formed by compositing the anionic MTM nanoplatelet filler in anionic and highly crystalline TOCN matrix. A composite film with 5% MTM content had Youngs modulus 18 GPa, tensile strength 509 MPa, work of fracture of 25.6 MJ m(-3), and oxygen permeability 0.006 mL μm m(-2) day(-1) kPa(-1) at 0% relative humidity, respectively, despite having a low density of 1.99 g cm(-3). As the MTM content in the TOCN/MTM composites was increased to 50%, light transmittance, tensile strength, and elongation at break decreased, while Youngs modulus was almost unchanged and oxygen barrier property was further improved to 0.0008 mL μm m(-2) day(-1) kPa(-1).

Superior reinforcement effect of TEMPO-oxidized cellulose nanofibrils in polystyrene matrix: optical, thermal, and mechanical studies.

Polystyrene (PS) composites reinforced with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (TOCNs) with various weight ratios were fabricated by casting and vacuum-drying mixtures of PS/N,N-dimethylformamide (DMF) solution and TOCN/DMF dispersion. TOCNs of 3 to 4 nm width were dispersed homogeneously at the individual nanofibril level in the PS matrix, such that the TOCN/PS nanocomposite films exhibited high optical transparencies and their tensile strengths, elastic moduli, and thermal dimensional stabilities increased with increasing TOCN content. Dynamic mechanical analysis showed that the storage modulus of the TOCN/PS films increased significantly with TOCN content above the glass-transition temperature of PS by the formation of an interfibrillar network structure of TOCNs in the PS matrix, based on percolation theory. The outstanding and effective polymer reinforcement by TOCNs results from their high aspect ratio, high crystallinity, and nanodispersibility in the PS matrix.

Surface engineering of ultrafine cellulose nanofibrils toward polymer nanocomposite materials.

Surface grafting of crystalline and ultrafine cellulose nanofibrils with poly(ethylene glycol) (PEG) chains via ionic bonds was achieved by a simple ion-exchange treatment. The PEG-grafted cellulose nanofibrils exhibited nanodispersibility in organic solvents such as chloroform, toluene, and tetrahydrofuran. Then, the PEG-grafted cellulose nanofibril/chloroform dispersion and poly(L-lactide) (PLLA)/chloroform solution were mixed, and the PEG-grafted cellulose nanofibril/PLLA composite films with various blend ratios were prepared by casting the mixtures on a plate and drying. The tensile strength, Youngs modulus, and work of fracture of the composite films were remarkably improved, despite low cellulose addition levels (<1 wt %). The highly efficient nanocomposite effect was explained in terms of achievement of nanodispersion states of the PEG-grafted cellulose nanofibrils in the PLLA matrix. Moreover, some attractive interactions mediated by the PEG chains were likely to be formed between the cellulose nanofibrils and PLLA molecules in the composites, additionally enhancing the efficient nanocomposite effect.

Selective permeation of hydrogen gas using cellulose nanofibril film.

Biobased membranes that can selectively permeate hydrogen gas have been developed from aqueous dispersions of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (TOCN) prepared from wood cellulose: TOCN-coated plastic films and self-standing TOCN films. Compared with TOCNs with sodium, lithium, potassium, and cesium carboxylate groups, TOCN with free carboxyl groups (TOCN-COOH) had much high and selective H2 gas permeation performance. Because permeabilities of H2, N2, O2, and CO2 gases through the membranes primarily depended on their kinetic diameters, the gas permeation behavior of the various TOCNs can be explained in terms of a diffusion mechanism. Thus, the selective H2 gas permeability for TOCN-COOH was probably due to a larger average size in free volume holes present between nanofibrils in the layer and film than those of other TOCNs with metal carboxylate groups. The obtained results indicate that TOCN-COOH membranes are applicable as biobased H2 gas separation membranes in fuel cell electric power generation systems.

Nano-dispersion of TEMPO-oxidized cellulose/aliphatic amine salts in isopropyl alcohol

Primary aliphatic amines were introduced into most of (>95%) carboxyl groups densely present on the TEMPO-oxidized cellulose nanofibril (TOCN) surfaces via carboxyl/amine salt formation in a water-isopropyl alcohol mixture. The carbon number of alkyl chain lengths introduced into TOCN varied using n-decyl-, n-dodecyl, n-tetradecyl-, n-hexadecyl- and n-octadecyl-amines. When n-dodecyl-, n-tetradecyl- and n-hexadecyl-amines were used for neutralization of carboxyl groups, the TOCN-COOH/amine salts were dispersed at the individual nanofibril level in pure isopropyl alcohol (IPA) by ultrasonication treatment, and gave stable and transparent IPA dispersions with birefringence when observed between cross polarizers. Flexible, highly transparent and surface-hydrophobic self-standing films of n-dodecylamine-treated TOCN-COOH (TOCN-COOH/C12-amine salt) were prepared by casting and drying of the dispersion. However, the introduction of abundant long-alkyl chains on the TOCN surfaces via the amine salt formation resulted in clearly lower mechanical and oxygen barrier properties of the films than those of TOCN-COONa films.

Low-Birefringent and Highly Tough Nanocellulose-Reinforced Cellulose Triacetate

Improvement of the mechanical and thermal properties of cellulose triacetate (CTA) films is required without sacrificing their optical properties. Here, poly(ethylene glycol) (PEG)-grafted cellulose nanofibril/CTA nanocomposite films were fabricated by casting and drying methods. The cellulose nanofibrils were prepared by 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation, and amine-terminated PEG chains were grafted onto the surfaces of the TEMPO-oxidized cellulose nanofibrils (TOCNs) by ionic bonds. Because of the nanosize effect of TOCNs with a uniform width of ∼3 nm, the PEG-TOCN/CTA nanocomposite films had high transparency and low birefringence. The grafted PEG chains enhanced the filler-matrix interactions and crystallization of matrix CTA molecules, resulting in the Youngs modulus and toughness of CTA film being significantly improved by PEG-grafted TOCN addition. The coefficient of thermal expansion of the original CTA film was mostly preserved even with the addition of PEG-grafted TOCNs. These results suggest that PEG-TOCNs are applicable to the reinforcement for transparent optical films.

Facile Route to Transparent, Strong, and Thermally Stable Nanocellulose/Polymer Nanocomposites from an Aqueous Pickering Emulsion

Cellulose nanofibril (CNF) is a promising nanofiller for polymer nanocomposite materials, and a critical challenge in designing these materials is organization of the nanostructure using a facile process. Here, we report a facile aqueous preparation process for nanostructured polystyrene (PS)/CNF composites via the formation of a CNF-stabilized Pickering emulsion. PS nanoparticles, with a narrow size distribution, were synthesized by free radical polymerization in water using CNF as a stabilizer. The nanoparticles were easily collected by filtration, and the resulting material had a composite structure of PS nanoparticles embedded in a CNF framework. The PS/CNF nanocomposite showed high optical transparency, strength, and thermal dimensional stability. Thus, this technique provides a simple and environmentally friendly method for the preparation of novel CNF/polymer nanocomposite materials.

Nanocellulose-stabilized Pickering emulsions and their applications

Abstract Pickering emulsion, which is an emulsion stabilized by solid particles, offers a wide range of potential applications because it generally provides a more stable system than surfactant-stabilized emulsion. Among various solid stabilizers, nanocellulose may open up new opportunities for future Pickering emulsions owing to its unique nanosizes, amphiphilicity, and other favorable properties (e.g. chemical stability, biodegradability, biocompatibility, and renewability). In this review, the preparation and properties of nanocellulose-stabilized Pickering emulsions are summarized. We also provide future perspectives on their applications, such as drug delivery, food, and composite materials.

Stability of (1→3)-β-polyglucuronic acid under various pH and temperature conditions.

Regioselective oxidation of C6 primary hydroxyls to carboxyls was applied to curdlan, to prepare a water-soluble (1→3)-β-polyglucuronic acid Na salt [(1,3)-β-PGluA], using a 4-acetamido-TEMPO/NaClO/NaClO₂ oxidation system at pH 4.7. Changes in the chemical structure and degree of polymerization of (1,3)-β-PGluA treated in water at various temperatures and pHs were studied to evaluate the stability of (1,3)-β-PGluA to these treatments. This polyuronic acid was found to be stable, without any depolymerization, to treatment in water at pHs 1-9 and room temperature for up to 128 h; slight depolymerization was observed at pHs 11 and 13. When heated in water at pH 1 and high temperatures (1,3)-β-PGluA molecules were randomly depolymerized by hydrolysis, primarily forming glucuronic acid. In contrast, dicarboxylic-acid-type monomers containing ethylene carbons were formed from the C1-carboxyl or C1 reducing ends of (1,3)-β-PGluA molecules by treatment under alkaline conditions; this was initiated by β-alkoxy elimination, similar to the peeling-off reaction of cellulose.

Tailoring Nanocellulose–Cellulose Triacetate Interfaces by Varying the Surface Grafting Density of Poly(ethylene glycol)

Careful design of the structures of interfaces between nanofillers and polymer matrices can significantly improve the mechanical and thermal properties of the overall nanocomposites. Here, we investigate how the grafting density on the surface of nanocelluloses influences the properties of nanocellulose/cellulose triacetate (CTA) composites. The surface of nanocellulose, which was prepared by 2,2,6,6-tetramethylpiperidine-1-oxyl oxidation, was modified with long poly(ethylene glycol) (PEG) chains at different grafting densities. The PEG-grafted nanocelluloses were homogeneously embedded in CTA matrices. The mechanical and thermal properties of the nanocomposites were characterized. Increasing the grafting density caused the soft PEG chains to form denser and thicker layers around the rigid nanocelluloses. The PEG layers were not completely miscible with the CTA matrix. This structure considerably enhanced the energy dissipation by allowing sliding at the interface, which increased the toughness of the nanocomposites. The thermal and mechanical properties of the composites could be tailored by controlling the grafting density. These findings provide a deeper understanding about interfacial design for nanocellulose-based composite materials.