Accelerated Design of Ultra-High-Performance Aramid Copolymers via a High-Throughput Screening Approach.

Developing advanced materials, such as functional polymers, poses a significant challenge as a result of the vastness of the material space that needs to be explored, which could potentially be infinite in principle. We propose a data-driven high-throughput screening approach coupled with molecular dynamics (MD) simulations to address this issue in the design of high-performance co-polymerized aramid fibers. We aimed to identify diamine monomers that could replace 3,4'-oxydianiline in Technora from a large-scale set (1 920 304) of possible monomers that were prepared from the PubChem database. We initially screened these monomers using a cheminformatics-based approach, considering four criteria: complexity, neutrality, linearity, and gyration radius of the molecule. Then, we performed subsequent screening based on MD simulations to estimate interchain interaction energies under both stretched and melted conditions and tensile strength simulations. Our screening approach successfully identified 31 promising and novel diamine monomers for aramid copolymers. This demonstrates the potential and effectiveness of our approach as a promising protocol for exploring targeted chemical spaces in designing novel monomers for high-performance aramid fibers and possibly other advanced polymers.

Molecular Dynamics Study of Cellulose Nanofiber Alignment under an Electric Field.

The alignment of cellulose by an electric field is an interesting subject for cellulose material processing and its applications. This paper reports an atomistic molecular dynamics simulation of the crystalline cellulose nanofiber (CNF) model in varying electric field directions and strengths. GROMACS software was used to study crystalline cellulose 1ß consisting of 18 chains in an aqueous environment at room temperature, and an electric field was applied along the cellulose chain direction and the perpendicular direction with varying field strength. The root-mean-square displacement, radius of gyration, end-to-end length, and hydrogen bond population of the crystalline CNF model were analyzed to determine the effects of the applied electric field on the structure of the CNF model. The results suggest that the nanosecond electric field can induce the orientation of the CNF along the applied electric field direction. The alignment rate and ability to maintain the alignment depend on the electric field strength. Analysis of the radius of gyration, end-to-end length, and bond lengths for intrachain and interchain hydrogen bonds revealed no significant effect on the cellulose structure. Cellulose alignment in an electric field has the potential to broaden the design of electric field-induced processing techniques for cellulose filaments, thin films, and electro-active cellulose composites.

Modulation of interfacial interactions toward strong and tough cellulose nanofiber-based transparent thin films with antifogging feature.

Cross-linking is often performed to overcome the weak mechanical properties of native polymer films in order to expand their functional properties and applications. While this approach offers enhanced strength to the film, the film also suffers from low flexibility, low toughness and high brittleness. However, in view of the growing demand for strong and tough transparent thin films, this article reported our study to develop films made from cellulose nanofiber (CNF) via tailoring the interfacial bonding interactions through the application of glycerol (Gly) and glutaraldehyde (GA), which functioned as a plasticizer and cross-linking agent, respectively. Among the prepared films, the 10GA-8Gly-CNF film exhibited the best results with regard to the enhancement in the tensile strength (21.1%), Young's modulus (10.6%), elongation at break (100%) and toughness (32.7%), as compared to the native CNF film. Importantly, treating the surface of the film to radiofrequency oxygen plasma endowed the film with antifogging property, without compromising the optical clarity.

Environment-Friendly Zinc Oxide Nanorods-Grown Cellulose Nanofiber Nanocomposite and Its Electromechanical and UV Sensing Behaviors.

This paper reports a genuine environment-friendly hybrid nanocomposite made by growing zinc oxide (ZnO) nanorods on cellulose nanofiber (CNF) film. The nanocomposite preparation, characterizations, electromechanical property, and ultraviolet (UV) sensing performance are explained. CNF was extracted from the pulp by combining the 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) oxidation and the aqueous counter collision (ACC) methods. The CNF film was fabricated using doctor blade casting, and ZnO nanorods were grown on the CNF film by seeding and by a hydrothermal method. Morphologies, optical transparency, mechanical and electromechanical properties, and UV sensing properties were examined. The nanocomposite's optical transparency was more than 80%, and the piezoelectric charge constant d31 was 200 times larger than the CNF film. The UV sensing performance of the prepared ZnO-CNF nanocomposites was tested in terms of ZnO concentration, UV irradiance intensity, exposure side, and electrode materials. A large aspect ratio of ZnO nanorods and a work function gap between ZnO nanorods and the electrode material are essential for improving the UV sensing performance. However, these conditions should be compromised with transparency. The use of CNF for ZnO-cellulose hybrid nanocomposite is beneficial not only for electromechanical and UV sensing properties but also for high mechanical properties, renewability, biocompatibility, flexibility, non-toxicity, and transparency.

All-biobased transparent-wood: A new approach and its environmental-friendly packaging application.

Transparent-wood (TW) is an emerging research topic that can be applied to biobased products. However, it is necessary to fill pores in TW with natural substances to prepare all-biobased TW. This paper reports an all-biobased TW by infiltrating cellulose nanofiber (CNF) and chitosan (CTS) suspensions into the bleached wood. CNF was isolated by combining the chemical and physical methods, and CTS was dissolved in acetic acid, and they were infiltrated into the pores of the bleached Fir veneer wood using a vacuum jar. The CNF and chitosan effects on the mechanical properties of the TW were studied, and the morphologies, crystallinity index, water contact angle, antioxidant, thermal degradation, and UV-shielding properties were investigated. The prepared TW showed 80 % total transmittance and 30-60 % haze, suitable for solar cell application. The all-biobased TW showed good thermal stability up to 315 °C and excellent UV shielding property for UV-B and UV-C. The antioxidant property of the CTS-TW significantly increased as compared to the original wood. The CNF-TW showed considerable tensile strength and yield strength of more than 200 % improved from the original wood. The potential for environment-friendly packaging applications was demonstrated by making a bag, medicine packaging, and straw for a drink.

Steered Pull Simulation to Determine Nanomechanical Properties of Cellulose Nanofiber.

Cellulose nanofiber (CNF) exhibits excellent mechanical properties, which has been extensively proven through experimental techniques. However, understanding the mechanisms and the inherent structural behavior of cellulose is important in its vastly growing research areas of applications. This study focuses on taking a look into what happens to the atomic molecular interactions of CNF, mainly hydrogen bond, in the presence of external force. This paper investigates the hydrogen bond disparity within CNF structure. To achieve this, molecular dynamics simulations of cellulose I ß nanofibers are carried out in equilibrated conditions in water using GROMACS software in conjunction with OPLS-AA force field. It is noted that the hydrogen bonds within the CNF are disrupted when a pulling force is applied. The simulated Young's modulus of CNF is found to be 161 GPa. A simulated shear within the cellulose chains presents a trend with more hydrogen bond disruptions at higher forces.

Electroactive Hydrogels Made with Polyvinyl Alcohol/Cellulose Nanocrystals.

This paper reports a nontoxic, soft and electroactive hydrogel made with polyvinyl alcohol (PVA) and cellulose nanocrystal (CNC). The CNC incorporating PVA-CNC hydrogels were prepared using a freeze⁻thaw technique with different CNC concentrations. Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray diffraction and scanning electron microscopy results proved the good miscibility of CNCs with PVA. The optical transparency, water uptake capacity and mechanical properties of the prepared hydrogels were investigated in this study. The CNC incorporating PVA-CNC hydrogels showed improved displacement output in the presence of an electric field and the displacement increased with an increase in the CNC concentration. The possible actuation mechanism was an electrostatic effect and the displacement improvement of the hydrogel associated with its enhanced dielectric properties and softness. Since the prepared PVA-CNC hydrogel is nontoxic and electroactive, it can be used for biomimetic soft robots, actively reconfigurable lenses and active drug-release applications.