Rheological Percolation of Cellulose Nanocrystals in Biodegradable Poly(butylene succinate) Nanocomposites: A Novel Approach for Tailoring the Mechanical and Hydrolytic Properties.

Although biodegradable plastics are gradually emerging as an effective solution to alleviate the burgeoning plastic pollution, their performance is currently trivial for commercialization. A proposed two-pronged strategy to overcome this limitation includes (1) preparation of the nanocomposites from biorenewable nano-fillers to preserve their biodegradability and (2) tailoring their properties to meet the diverse demands in various applications. Herein, we report the preparation of biodegradable nanocomposites composed of poly(butylene succinate) (PBS) and cellulose nanocrystals (CNCs) (loading of 0.2-3.0 wt%) and propose a rheological strategy to tailor their performances. Depending on the shear frequencies, the rheological evaluation revealed two percolation thresholds at approximately 0.8 and 1.5 wt%. At high shear frequencies, the disappearance of the first threshold (0.8 wt%) and the sole persistence of the second one (1.5 wt%) indicated the collapse of the immature network of partially interconnected CNCs. The tensile and hydrolytic properties of the nanocomposites were found to undergo drastic changes at the thresholds. The tensile strength increased by 17% (from 33.3 to 39.2 MPa) up to 0.8 wt% CNC loading. However, the reinforcing efficiency of CNC decreases sharply with further incorporation, reaching nearly zero at 1.5 wt%. On the other hand, hydrolytic degradation of the nanocomposites was rapidly accelerated above 1.5 wt% CNC loading. Therefore, a thorough understanding of the rheological properties of nanocomposites is essential for the design and development of materials with tailored properties.

Redox-Triggered Coloration Mechanism of Electrically Tunable Colloidal Photonic Crystals.

Electrically tunable colloidal photonic crystals (ETPCs) have been investigated because of several merits such as easy color tunability, no discoloration, and clear color. The coloration mechanism of ETPCs has been explained in terms of only the electric field. Herein, we report on a new mechanism: electric field plus redox reaction. Specifically, the coloration behavior of ETPCs was investigated under electrically conductive or insulated conditions using current-voltage, cyclic voltammetry, and zeta potential measurements, as well as scanning electron microscopy. Electrophoretic movement of ETPC particles toward the positive electrode was caused by the electric field due to the particles' negative surface charge. At the positive electrode, ETPC particles lost their electrons and formed a colloidal crystal structure. Finally, an ETPC transparent tube device was constructed to demonstrate the coloration mechanism.

Fabrication of double-tubular carbon nanofibers using quadruple coaxial electrospinning.

This work reports the fabrication of double-tubular (or tube-in-tube) carbon nanofibers (CNFs). Tetra-layered nanofibers were manufactured using coaxial electrospinning with a concentric quadruple cylindrical nozzle system. Subsequent heat treatment eroded the first and third layers and converted the second and fourth layers into the carbonized structure, resulting in double-tubular CNFs. The morphologies and microstructures of the two tubes in the CNFs were investigated, revealing that the outer layer possessed denser and higher quality carbon crystals due to the coaxial electrospinning mechanism. Nanoparticles were readily incorporated between the two tubes in the double-tubular CNFs, providing a method for developing new multi-functional one dimensional materials.

Tailoring Lithium Horizontal Deposition for Long-Lasting High-Loading NCA (≥5 mA h cm-2)||Lithium-Metal Full Cells in Carbonate Electrolytes.

We report a design for a synergistic lithium (Li) metal hosting layer for high-loading Li(Ni,Co,Al)O2 (NCA) (≥5 mA h cm-2)||Li-metal full cells in carbonate electrolytes. Based on density functional theory calculations, the hosting layer was designed as a three-dimensional silver/carbon composite nanofiber (Ag/CNF) network with high Li affinity and a platinum (Pt)-coated polypropylene separator with low Li affinity. This design enabled the tailoring of horizontal Li deposition on the Ag/CNF hosting layer. The Li deposition behavior modulated by the hosting layer was thoroughly examined based on the initial Li deposition and cycling behaviors of the Li||Li symmetric cell configuration. Cryogenic focused-ion beam cross-sectional images of the cycled Li anodes clearly demonstrated that dense lithium deposition was enabled by the synergistic hosting layer high-loading NCA (≥5 mA h cm-2)||Li-metal full cells. When the hosting layer was used, the average cycling performance improved by 78.27% under various cycling conditions. Our work demonstrates that the synergistic hosting layer design is a fruitful pathway to accelerate the commercialization of high-energy-density Li-metal batteries in carbonate electrolytes.

Biodegradable, Efficient, and Breathable Multi-Use Face Mask Filter.

The demand for face masks is increasing exponentially due to the coronavirus pandemic and issues associated with airborne particulate matter (PM). However, both conventional electrostatic- and nanosieve-based mask filters are single-use and are not degradable or recyclable, which creates serious waste problems. In addition, the former loses function under humid conditions, while the latter operates with a significant air-pressure drop and suffers from relatively fast pore blockage. Herein, a biodegradable, moisture-resistant, highly breathable, and high-performance fibrous mask filter is developed. Briefly, two biodegradable microfiber and nanofiber mats are integrated into a Janus membrane filter and then coated by cationically charged chitosan nanowhiskers. This filter is as efficient as the commercial N95 filter and removes 98.3% of 2.5 µm PM. The nanofiber physically sieves fine PM and the microfiber provides a low pressure differential of 59 Pa, which is comfortable for human breathing. In contrast to the dramatic performance decline of the commercial N95 filter when exposed to moisture, this filter exhibits negligible performance loss and is therefore multi-usable because the permanent dipoles of the chitosan adsorb ultrafine PM (e.g., nitrogen and sulfur oxides). Importantly, this filter completely decomposes within 4 weeks in composting soil.

Recent Progress in Coaxial Electrospinning: New Parameters, Various Structures, and Wide Applications.

Electrospinning, a common method for synthesizing 1D nanostructures, has contributed to developments in the electrical, electrochemical, biomedical, and environmental fields. Recently, a coaxial electrospinning process has been used to fabricate new nanostructures with advanced performance, but intricate and delicate process conditions hinder reproducibility and mass production. Herein, recent progress in new emerging parameters for successful coaxial electrospinning, and the various nanostructures and critical application areas resulting from these activities. Relationships between the new parameters and final product characteristics are described, new possibilities for nanostructures achievable via coaxial electrospinning are identified, and new research directions with a view to future applications are suggested.

New electrospinning nozzle to reduce jet instability and its application to manufacture of multi-layered nanofibers.

A new nozzle system for the efficient production of multi-layered nanofibers through electrospinning is reported. Developed a decade ago, the commonly used coaxial nozzle system consisting of two concentric cylindrical needles has remained unchanged, despite recent advances in multi-layered, multi-functional nanofibers. Here, we demonstrate a core-cut nozzle system, in which the exit pipe of the core nozzle is removed such that the core fluid can form an envelope inside the shell solution. This configuration effectively improves the coaxial electrospinning behavior of two fluids and significantly reduces the jet instability, which was proved by finite element simulation. The proposed electrospinning nozzle system was then used to fabricate bi- and tri-layered carbon nanofibers.

Effects of substrate on piezoelectricity of electrospun poly(vinylidene fluoride)-nanofiber-based energy generators.

We report the effects of various substrates and substrate thicknesses on electrospun poly(vinylidene fluoride) (PVDF)-nanofiber-based energy harvesters. The electrospun PVDF nanofibers showed an average diameter of 84.6 ± 23.5 nm. A high relative ß-phase fraction (85.2%) was achieved by applying high voltage during electrospinning. The prepared PVDF nanofibers thus generated considerable piezoelectric potential in accordance with the sound-driven mechanical vibrations of the substrates. Slide glass, poly(ethylene terephthalate), poly(ethylene naphthalate), and paper substrates were used to investigate the effects of the intrinsic and extrinsic substrate properties on the piezoelectricity of the energy harvesters. The thinnest paper substrate (66 µm) with a moderate Young's modulus showed the highest voltage output (0.4885 V). We used high-performance 76, 66, and 33 µm thick papers to determine the effect of paper thickness on the output voltage. The thinnest paper substrate resulted in the highest voltage output (0.7781 V), and the numerical analyses of the sound-driven mechanical deformation strongly support the hypothesis that substrate thickness has a considerable effect on piezoelectric performance.

Novel multi-layered 1-D nanostructure exhibiting the theoretical capacity of silicon for a super-enhanced lithium-ion battery.

Silicon/carbon (Si/C) nanocomposites have recently received much attention as Li-ion battery negative electrodes due to their mutual synergetic effects in capacity and mechanical integrity. The contribution of Si to the total capacity of the Si/C nanocomposites determines their structural efficiency. Herein, we report on a multi-layered, one-dimensional nanostructure that exhibits the theoretical specific capacity of Si in the nanocomposite. Concentrically tri-layered, compartmentalized, C-core/Si-medium/C-shell nanofibers were fabricated by triple coaxial electrospinning. The pulverization of Si was accommodated inside the C-shell, whereas the conductive pathway of the Li-ions and electrons was provided by the C-core, which was proven by ex situ Raman spectroscopy. The compartmentalized Si in between the C-core and C-shell led to excellent specific capacity at a high current rate (>820 mA h g(-1) at 12000 mA g(-1)) and the realization of the theoretical specific capacity of the Li15Si4 phase of Si nanoparticles (3627 mA h g(-1)). The electrochemical characterization and inductively coupled plasma-atomic emission spectrometry provided direct evidence of full participation of Si in the electrochemical reactions.