Self-healing, flame-retardant, and antimicrobial chitosan-based dynamic covalent hydrogels.

This study reports the fabrication of chitosan-based hydrogels with potential to be applied as a flame-retardant coating on skin or other surfaces. These hydrogels possess remarkable antimicrobial properties that are highly desirable for the protection of epidermises. Hydrogels in this study were prepared via the cross-linking reaction of chitosan with a vanillin-based cross linker containing flame-retarding moieties through Schiff's base reaction. The synthesized hydrogels possess imine linkages enabling them to self-heal at room temperature. Self-healing abilities offered these hydrogels the ability to protect the skin for a longer time. One flame retarding mechanism of these hydrogels was by retaining the water in their polymeric network; thus, the role of bound and unbound water molecules was studied using DSC and Raman spectroscopy. The hydrogels synthesized in this study retained their flame-retarding properties even after drying due to the charring process that inhibited the pyrolysis process. Therefore, these chitosan-based hydrogels are able to prolong the protection time against fire.

Antagonistically Functionalized Diatom Biosilica for Bio-Triboelectric Generators.

Although biomaterial-based triboelectric nanogenerators (Bio-TENGs) for use in wearable electronics and implantable sensors have been developed, power generation is not suitable for satisfying the basic requirements for practical applications. Here, to greatly enhance output performances of Bio-TENG devices, an antagonistic approach of diatom frustules (DFs) with amine and fluorine chemical functionalizations is reported. The DFs are treated with piranha solution to increase the density of hydroxyl groups and tribo-positive and tribo-negative composite films are designed with antagonistically functionalized DFs. The tribo-positive composites having electron donating functionality consist of aminated DFs and cellulose nanocrystals (CNCs), while the tribo-negative composite is composed of fluorinated DFs and polydimethylsiloxane (PDMS). An antagonistically and chemically functionalized TENG (ACF TENG) with an efficient contact area of 9.6 cm2 under a force of 8 N and a frequency of 5 Hz exhibits an output voltage of 248 V, a short-circuit current of 16.4 µA, and a power density of 2.01 W m-2 , which is 16.6 times higher than a reference (CNC:PDMS) TENG. This study shows a simple antagonistic approach for chemical functionalization as an efficient method to manipulate the tribo-polarity of bio-additives for enhancing power generation of Bio-TENGs.

Electro-Active and Photo-Active Vanadium Oxide Nanowire Thermo-Hygroscopic Actuators for Kirigami Pop-up.

Emerging technologies such as soft robotics, active biomedical devices, wearable electronics, haptic feedback systems, and healthcare systems require high-fidelity soft actuators showing reliable responses under multi-stimuli. In this study, the authors report an electro-active and photo-active soft actuator based on a vanadium oxide nanowire (VONW) hybrid film with greatly improved actuation performances. The VONWs directly grown on a cellulose fiber network increase the surface area up to 30-fold and boost the hydrophilicity owing to the presence of oxygen-rich functional groups in the nanowire surfaces. Taking advantage of the high surface area and hydrophilicity of VONWs, a soft thermo-hygroscopic VONW actuator capable of being controlled by both light and electric sources shows greatly enhanced actuation deformation by almost 70% and increased actuation speed over 3 times during natural convection cooling. Most importantly, the proposed VONW actuator exhibits a remarkably improved blocking force of up to 200% compared with a bare paper actuator under light stimulation, allowing them to realize a complex kirigami pop-up and to accomplish repeatable shape transformation from a 2D planar surface to a 3D configuration.

Improving the Barrier Properties of Packaging Paper by Polyvinyl Alcohol Based Polymer Coating-Effect of the Base Paper and Nanoclay.

The poor barrier properties and hygroscopic nature of cellulosic paper impede the wide application of cellulosic paper as a packaging material. Herein, a polyvinyl alcohol (PVA)-based polymer coating was used to improve the barrier performance of paper through its good ability to form a film. Alkyl ketene dimer (AKD) was used to enhance the water resistance. The effect of the absorptive characteristics of the base paper on the barrier properties was explored, and it was shown that surface-sized base paper provides a better barrier performance than unsized base paper. Nanoclay (Cloisite Na+) was used in the coating formulation to further enhance the barrier performance. The results show that the coating of PVA/AKD/nanoclay dispersion noticeably improved the barrier performance of the paper. The water vapor transmission rate of the base paper was 533 g/m2·day, and it decreased sharply to 1.3 g/m2·day after the application of a double coating because of the complete coverage of the base paper by the PVA-based polymer coating. The coated paper had excellent water resistance owing to its high water contact angle of around 100°. The grease resistance and mechanical properties of the base paper also improved after coating. This work may provide inspiration for improving the barrier properties of packaging paper through the selection of a suitable base paper and coating formulation.

The Effect of a Polymer-Stabilized Latex Cobinder on the Optical and Strength Properties of Pigment Coating Layers.

Coated paper with a porous coating layer may have enhanced light-scattering ability and thus favorable optical properties. However, the increased porosity of such a coating layer is likely to decrease the strength of the coated paper, thereby adversely affecting the quality of the paper in the printing and converting processes. In this research, polymer-stabilized (PS) latex was prepared and used as a cobinder for the pigment coating of the paper. The PS latex particles were colloidally stabilized by a 3:1 mixture of starch and polyvinyl alcohol. The influence of the PS latex cobinder on the viscosity, sedimentation, and consolidation of coating colors was investigated. In addition, the effect of the cobinder on the properties of coating layers, namely, their porosity and surface, optical, and tensile properties, was examined. The results revealed that the PS latex cobinder formed microstructures in the coating colors and affected their viscosity. The addition of PS latex also led to enhanced interactions between coating color components, which affected the consolidation of the coating color, resulting in the formation of dried coating layers with greater porosity and improved optical properties (i.e., higher brightness and opacity) relative to coatings without the PS latex cobinder. Furthermore, the addition of PS latex improved the tensile strength of the coating layers, which was attributable to the small size and the polymeric protective shell of the cobinder particles. Thus, these results show that this PS latex cobinder has the potential to be used for the production of high-quality coated paper products.

Diatom Bio-Silica and Cellulose Nanofibril for Bio-Triboelectric Nanogenerators and Self-Powered Breath Monitoring Masks.

The application of biodegradable and biocompatible materials to triboelectric nanogenerators (TENGs) for harvesting energy from motions of the human body has been attracting significant research interest. Herein, we report diatom bio-silica as a biomaterial additive to enhance the output performance of cellulose nanofibril (CNF)-based TENGs. Diatom frustules (DFs), which are tribopositive bio-silica having hierarchically porous three-dimensional structures and high surface area, have hydrogen bonds with CNFs, resulting in enhanced electron-donating capability and a more roughened surface of the DF-CNF composite film. Hence, DFs were applied to form a tribopositive composite film with CNFs. The DF-CNF biocomposite film is mechanically strong, electron-rich, low-cost, and frictionally rough. The DF-CNF TENG showed an output voltage of 388 V and time-averaged power of 85.5 mW/m2 in the contact-separation mode with an efficient contact area of 4.9 cm2, and the generated power was sufficient for instantaneous illumination of 102 light-emitting diodes. In addition, a cytotoxicity study and biocompatibility tests on rabbit skin suggested that the DF-CNF composite was biologically safe. Moreover, a practical application of the DF-CNF TENG was examined with a self-powered smart mask for human breathing monitoring. This study not only suggests high output performance of biomaterial-based TENGs but also presents the diverse advantages of the DFs in human body-related applications such as self-powered health monitoring masks, skin-attachable power generators, and tactile feedback systems.

Development and Application of Nanosized Polymer-Stabilized Cobinders and Their Effect on the Viscoelastic Properties and Foaming Tendencies of Coating Colors.

Polymer latexes have long been used as coating binders by various branches of industry due to their capacity to adhere coating components and increase the strength of the dried final coatings. In addition, these latexes have been known to affect the rheology of coating dispersions. Currently, emulsion polymerization is the most widely used method of producing polymer latexes. While the stability of these latexes is primarily provided by electrostatic repulsion between surfactants, this property also causes foaming problems during coating processes. In this research, these problems were addressed by preparing polymer-stabilized (PS) latexes that contained different concentrations of acrylic acid. Steric protection of the latexes was provided by a protective shell consisting of starch and poly(vinyl alcohol) (PVA). The viscosity, particle size, ζ-potential, and viscoelastic behavior of the prepared latexes were investigated as a function of pH, and their surface tension and foaming tendencies were evaluated. The latexes were applied as coating cobinders in calcium carbonate and clay coating dispersions, and the viscoelastic properties, surface tensions, and foaming tendencies of these mixtures were studied. The presence of acrylic acid monomers was found to be an important factor affecting the viscosity, particle size, and ζ-potential of the PS latexes prepared in this work, which were further found to generate less foam than comparable emulsion-polymerized latexes. Finally, coating color viscoelastic properties were modified via the partial substitution of styrene-butadiene (S/B) latexes with PS latexes.

Electrochemical activity of Samarium on starch-derived porous carbon: rechargeable Li- and Al-ion batteries.

Rechargeable metal-ion batteries are considered promising electric storage systems to meet the emerging demand from electric vehicles, electronics, and electric grids. Thus far, secondary Li-ion batteries (LIBs) have seen great advances in terms of both their energy and their power density. However, safety issues remain a challenge. Therefore, rechargeable Al-ion batteries (AIBs) with a highly reliable safety advantage and active electrochemical performances have gathered intensive attention. However, the common issue for these two metal-ion batteries is the lack of cathode materials. Many advanced electrode materials reported provide greatly enhanced electrochemical properties. However, their inherent disadvantages-such as complicated fabrication procedures, restricted manufacturing parameters, and the requirement of expensive instruments-limits their potential for further applications. In this work, we demonstrate the high electrochemical activity of the lanthanide element, Sm, towards storing charges when used in both LIBs and AIBs. Lanthanide elements are often overlooked; however, they generally have attractive electrochemical properties owing to their unpaired electrons. We employed starch as both a low-cost carbon source and as a three-dimensional support for Sm metal nanoparticles. The composite product is fabricated using a one-pot wet-chemical method, followed by a simultaneous carbonization process. As a result, highly improved electrochemical properties are obtained when it is used as a cathode material for both LIBs and AIBs when compared to bare starch-derived C. Our results may introduce a new avenue toward the design of high-performance electrode materials for LIBs and AIBs.

Recycling of isopropanol for cost-effective, environmentally friendly production of carboxymethylated cellulose nanofibrils.

An approach to recycling isopropanol used in the carboxymethylation of pulp fiber was investigated as a cost-effective and environmentally friendly method of producing cellulose nanofibrils (CNF). Carboxymethylation of pulp fiber was carried out using isopropanol (IPA) as the sole solvent. IPA was recovered after carboxymethylation reaction and recycled in the next carboxymethylation reaction. Simple recycling of IPA decreased the reaction efficiency of carboxymethylation due to the increase of water content in the IPA. To dehydrate the recovered IPA, a 4 Å molecular sieve was used as a drying material. It was shown that dehydration restored carboxymethylation efficiency to the same level as when fresh IPA was used. The characteristics of the carboxymethylated CNFs produced using the recycled IPA were evaluated, including fibrillation tendency, average width, and width distribution, and it was shown that the use of recycled IPA after dehydration treatment did not cause any changes in carboxymethylated CNF properties. Recycling IPA after simple dehydration using a molecular sieve is thus a cost-effective and environmentally friendly method of producing carboxymethylated CNF.