Cellulose, the chain of glucose residues easily obtained from nature, is the most common natural polymer. Owing to its own unique material properties, compared to the conventional usage, nanocellulose (NC) with a crystalline structure can be considered to be used in various industrial applications. As a novel sustainable future material, we review the recent achievements of NC from the view point of material extraction and the composite processes to some extended important applications. While the mechanical properties of NCs and the energy consumption during their composite processing are the key considerations, their application potentials have never been limited to mechanical or commodity products as conventional celluloses. In the latter part of this review, emerging engineering applications of NCs such as energy storage, flexible electronics, and smart materials will be further discussed for readers searching future high-end eco-friendly functional materials. Also some suggestions for potential applications will be also discussed.
Natural melanins are biocompatible conductors with versatile functionalities. Here, we report fabrication of multifunctional poly(vinyl alcohol)/melanin nanocomposites by layer-by-layer (LBL) assembly using melanin nanoparticles (MNPs) directly extracted from sepia officinalis inks. The LBL assembly offers facile manipulation of nanotextures as well as nm-thickness control of the macroscale film by varying solvent qualities. The time-resolved absorption was monitored during the process and quantitatively studied by fractal dimension and lacunarity analysis. The capability of nanoarchitecturing provides confirmation of complete monolayer formation and leads to tunable iridescent reflective colors of the MNP films. In addition, the MNP films have durable electrochemical conductivities as evidenced by enhanced charge storage capacities for 1000 cycles. Moreover, the MNP covered ITO (indium tin oxide) substrates significantly reduced secretion of inflammatory cytokines, TNF-α, by raw 264.7 macrophage cells compared to bare ITO, by a factor of 5 and 1.8 with and without lipopolysaccharide endotoxins, respectively. These results highlight the optoelectronic device-level tunability along with the anti-inflammatory biocompatibility of the MNP LBL film. This combination of performance should make these films particularly interesting for bioelectronic device applications such as electroceuticals, artificial bionic organs, biosensors, and implantable devices.
The reinforcement of polymer nanocomposites can be achieved through alignment or percolation of cellulose nanocrystals (CNCs). Here, we compare the efficacy of these reinforcement mechanisms in thermoplastic polyurethane (PU) elastomer nanocomposites containing thermally stable cotton CNCs. CNC alignment was achieved by melt spinning nanocomposite fibers, while a percolating CNC network was generated by solvent casting nanocomposite films with CNC contents up to 20 wt %. While in films both the CNCs and the PU matrix were entirely isotropic at all concentrations as confirmed by wide-angle X-ray scattering and birefringence analysis, the CNCs in the fibers exhibited a preferential orientation, which improved with increasing CNC concentration. Increasing the CNC concentration in the fibers reduces, however, the alignment of the PU chains, resulting in an entirely isotropic PU matrix at high CNC contents. The mechanical properties of films and fibers were evaluated using stress− strain measurements. Nanocomposite fibers with low CNC content exhibited superior stiffness, extensibility, and strength compared to the films, while the films displayed superior mechanical properties at high CNC concentrations. These findings are rationalized using common semiempirical models describing the reinforcing effects of CNC alignment in fibers (Halpin−Tsai) and CNC percolation in films (percolation model). The formation of a percolating CNC network leads to a stronger reinforcement than CNC alignment, as the reinforcing effect of the latter is limited by the comparably low aspect ratio of CNCs extracted from cotton. As a consequence, above the percolation threshold for cotton CNCs, isotropic nanocomposite PU films show a higher stiffness than aligned nanocomposite PU fibers.
This paper highlights the influence of peptide secondary structure on the shape memory behaviour of peptidic polyureas, driven by hydrogen bonding arrangement and microphase-separated morphology.
thermal instabilities of liquid electrolytes can cause significant drawbacks, particularly for safety. Solid-state electrolyte can overcome these limitations. Typically, solid-state electrolytes have five classifications based on the material constituents: [1] inorganic electrolytes, polymer electrolytes, hybrid electrolytes, gel-polymer electrolytes, and hybrid quasisolid electrolytes. Hybrid electrolytes Solid-state electrolytes can alleviate the safety issues of electrochemical energy systems related to chemical and thermal instabilities of liquid electrolytes. While a liquid provides seamless ionic transport with almost perfect wettability between electrodes, a solid-state electrolyte needs to demonstrate at least comparable electrochemical performance to liquid electrolytes as well as mechanical robustness and flexibility. Here, the facile preparation of montmorillonite (MMT)/dimethyl sulfoxide (DMSO) nanocomposites is reported, which show high ionic conductivities, mechanical strengths, and thermal stabilities by forming nacre-mimetic "brick-and-mortar" structures. The molecularly confined structures of DMSO are confirmed by X-ray diffraction peaks with d-spacings of interplanar spacing that are slightly larger than MMTs. The MMT/DMSO composites have mechanical strengths and toughnesses of 55.3 ± 4.8 MPa and 210.2 ± 32.6 kJ m −2 , respectively. The ionic conductivity is ≈2 × 10 −4 S cm −1 at room temperature, and their thermal stability is in the range of −100 to 120 °C. The optical translucency, on-demand eco-degradability, and solution processability together make the MMT/DMSO composites unique materials with a wide range of solid-state electrochemical applications including batteries.
Amphiphilic polymer conetworks (APCNs) are polymer networks composed of hydrophilic and hydrophobic chain segments. Their applications range from soft contact lenses to membranes and biomaterials. APCNs based on polydimethylsiloxane (PDMS) and poly(2‐hydroxyethyl acrylate) are flexible and elastic in the dry and swollen state. However, they are not good at resisting deformation under load, i.e., their toughness is low. A bio‐inspired approach to reinforce APCNs is presented based on the incorporation of poly(β‐benzyl‐L‐aspartate) (PBLA) blocks between cross‐linking points and PDMS chain segments. The mechanical properties of the resulting peptide‐reinforced APCNs can be tailored by the secondary structure of the peptide chains (β‐sheets or a mixture of α‐helices and β‐sheets). Compared to non‐reinforced APCNs, the peptide‐reinforced networks have higher extensibility (53 vs. up to 341%), strength (0.71 ± 0.16 vs. 22.28 ± 2.81 MPa), and toughness (0.10 ± 0.04 vs. up to 4.85 ± 1.32 MJ m−3), as measured in their dry state. The PBLA peptides reversibly toughen and reinforce the APCNs, while other key material properties of APCNs are retained, such as optical transparency and swellability in water and organic solvents. This paves the way for applications of APCNs that benefit from significantly increased mechanical properties.
We report the electrospinning of mechanically-tunable, cellulose nanocrystal (CNC)-reinforced polyurethanes (PUs). Using high-aspect ratio CNCs from tunicates, the stiffness and strength of electrospun PU/CNC mats are shown to generally increase. Furthermore, by tuning the electrospinning conditions, fibrous PU/CNC mats were created with either aligned or non-aligned fibers, as confirmed by scanning electron microscopy. PU/CNC mats having fibers aligned in the strain direction were stiffer and stronger compared to mats containing non-aligned fibers. Interestingly, fiber alignment was accompanied by an anisotropic orientation of the CNCs, as confirmed by wide-angle X-ray scattering, implying their alignment additionally benefits both stiffness and strength of fibrous PU/CNC nanocomposite mats. These findings suggest that CNC alignment could serve as an additional reinforcement mechanism in the design of stronger fibrous nanocomposite mats.
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