Jingquan Han

Self-assembling behavior of cellulose nanoparticles during freeze-drying: effect of suspension concentration, particle size, crystal structure, and surface charge.

Cellulose nanocrystals and cellulose nanofibers with I and II crystalline allomorphs (designated as CNC I, CNC II, CNF I, and CNF II) were isolated from bleached wood fibers by alkaline pretreatment and acid hydrolysis. The effects of concentration, particle size, surface charge, and crystal structure on the lyophilization-induced self-assembly of cellulose particles in aqueous suspensions were studied. Within the concentration range of 0.5 to 1.0 wt %, cellulose particles self-organized into lamellar structured foam composed of aligned membrane layers with widths between 0.5 and 3 μm. At 0.05 wt %, CNC I, CNF I, CNC II, and CNF II self-assembled into oriented ultrafine fibers with mean diameters of 0.57, 1.02, 1.50, and 1.00 μm, respectively. The size of self-assembled fibers became larger when more hydroxyl groups and fewer sulfates (weaker electrostatic repulsion) were on cellulose surfaces. Possible formation mechanism was inferred from ice growth and interaction between cellulose nanoparticles in liquid-crystalline suspensions.

Characterization of cellulose II nanoparticles regenerated from 1-butyl-3-methylimidazolium chloride

Regenerated cellulose nanoparticles (RCNs) including both elongated fiber and spherical structures were prepared from microcrystalline cellulose (MCC) and cotton using 1-butyl-3-methylimidazolium chloride followed by high-pressure homogenization. The crystalline structure of RCNs was cellulose II in contrast to the cellulose I form of the starting materials. Also, the RCNs have decreased crystallinity and crystallite size. The elongated RCNs produced from cotton and MCC had average lengths of 123 ± 34 and 112 ± 42 nm, and mean widths of 12 ± 5 and 12 ± 3 nm, respectively. The average diameter of spherical RCNs from MCC was 118 ± 32nm. The dimensions of the various RCNs were all well fitted with an asymmetrical log-normal distribution function. The RCN has a two-step pyrolysis, different from raw MCC and cotton that have a one-step process.

High-water-content mouldable polyvinyl alcohol-borax hydrogels reinforced by well-dispersed cellulose nanoparticles: dynamic rheological properties and hydrogel formation mechanism.

Cellulose nanoparticle (CNP) reinforced polyvinyl alcohol-borax (PB) hydrogels were produced via a facile approach in an aqueous system. The effects of particle size, aspect ratio, crystal structure, and surface charge of CNPs on the rheological properties of the composite hydrogels were investigated. The rheological measurements confirmed the incorporation of well-dispersed CNPs to PB system significantly enhanced the viscoelasticity and stiffness of hydrogels. The obtained free-standing, high elasticity and mouldable hydrogels exhibited self-recovery under continuous step strain and thermo-reversibility under temperature sweep. With the addition of cellulose I nanofibers, a 19-fold increase in the high-frequency plateau of storage modulus was obtained compared with that of the pure PB. CNPs acted as multifunctional crosslinking agents and nanofillers to physically and chemically bridge the 3D network hydrogel. The plausible mechanism for the multi-complexation between CNPs, polyvinyl alcohol and borax was proposed to understand the relationship between the 3D network and hydrogel properties.

Characterization of cellulose I/II hybrid fibers isolated from energycane bagasse during the delignification process: Morphology, crystallinity and percentage estimation.

Cellulose I, cellulose II and cellulose I/II hybrid fibers were prepared from energycane bagasse using NaOH and NaClO2 treatments. The definitive defibrillation effect with an average width of 12±5μm was observed for the fibers treated with 20wt% NaOH for 10h and NaClO2 for 2h. The ribbon shaped cellulose I fibers were converted to a swollen state with a rougher surface by 20wt% NaOH treatment for 10h. The percentage of cellulose I decreased from 100% to 5%, and the corresponding CI values increased from 58.2% to 68.8% during the conversion from cellulose I to II. After further NaClO2 treatment, the CI values were decreased because of partial destruction of hydrogen bond network. XRD, NMR and FTIR results present the same trend in the degree of crystallization for all the samples.

Effect of Acid Hydrolysis Conditions on the Properties of Cellulose Nanoparticle-Reinforced Polymethylmethacrylate Composites

Cellulose nanoparticles (CNPs) were prepared from microcrystalline cellulose using two concentration levels of sulfuric acid (i.e., 48 wt% and 64 wt% with produced CNPs designated as CNPs-48 and CNPs-64, respectively) followed by high-pressure homogenization. CNP-reinforced polymethylmethacrylate (PMMA) composite films at various CNP loadings were made using solvent exchange and solution casting methods. The ultraviolet-visible (UV-vis) transmittance spectra between 400 and 800 nm showed that CNPs-64/PMMA composites had a significantly higher optical transmittance than that of CNPs-48/PMMA. Their transmittance decreased with increased CNP loadings. The addition of CNPs to the PMMA matrix reduced composite’s coefficient of thermal expansion (CTE), and CNPs-64/PMMA had a lower CTE than CNPs-48/PMMA at the same CNP level. Reinforcement effect was achieved with the addition of CNPs to the PMMA matrix, especially at higher temperature levels. CNPs-64/PMMA exhibited a higher storage modulus compared with CNPs-48/PMMA material. All CNP-reinforced composites showed higher Young’s modulus and tensile strengths than pure PMMA. The effect increased with increased CNP loadings in the PMMA matrix for both CNPs-64/PMMA and CNPs-48/PMMA composites. CNPs affected the Young’s modulus more than they affected the tensile strength.

Cellulose nanofibers reinforced sodium alginate-polyvinyl alcohol hydrogels: Core-shell structure formation and property characterization

Core-shell structured hydrogels consisting of a flexible interpenetrating polymer network (IPN) core and a rigid semi-IPN shell were prepared through chemical crosslinking of polyvinyl alcohol (PVA) and sodium alginate (SA) with Ca(2+) and glutaraldehyde. Short cellulose nanofibers (CNFs) extracted from energycane bagasse were incorporated in the hydrogel. The shell was micro-porous and the core was macro-porous. The hydrogels could be used in multiple adsorption-desorption cycles for dyes, and the maximum methyl blue adsorption capacity had a 10% increase after incorporating CNFs. The homogeneous distribution of CNFs in PVA-SA matrix generated additional hydrogen bonds among the polymer molecular chains, resulting in enhanced density, viscoelasticity, and mechanical strength for the hydrogel. Specifically, the compressive strength of the hydrogel reached 79.5kPa, 3.2 times higher than that of the neat hydrogel.

Nanocellulose-Mediated Electroconductive Self-Healing Hydrogels with High Strength, Plasticity, Viscoelasticity, Stretchability, and Biocompatibility toward Multifunctional Applications

Conducting polymer hydrogels (CPHs) have emerged as a fascinating class of smart soft matters important for various advanced applications. However, achieving the synergistic characteristics of conductivity, self-healing ability, biocompatibility, viscoelasticity, and high mechanical performance still remains a critical challenge. Here, we develop for the first time a type of multifunctional hybrid CPHs based on a viscoelastic polyvinyl alcohol (PVA)-borax (PB) gel matrix and nanostructured CNFs-PPy (cellulose nanofibers-polypyrrole) complexes that synergizes the biotemplate role of CNFs and the conductive nature of PPy. The CNF-PPy complexes are synthesized through in situ oxidative polymerization of pyrrole on the surface of CNF templates, which are further well-dispersed into the PB matrix to synthesize homogeneous CNF-PPy/PB hybrid hydrogels. The CNF-PPy complexes not only tangle with PVA chains though hydrogen bonds, but also form reversibly cross-linked complexes with borate ions. The multi-complexation between each component leads to the formation of a hierarchical three-dimensional network. The CNF-PPy/PB-3 hydrogel prepared by 2.0 wt % of PVA, 0.4 wt % of borax, and CNF-PPy complexes with a mass ratio of 3.75/1 exhibits the highest viscoelasticity and mechanical strength. Because of a combined reinforcing and conductive network inside the hydrogel, its maximum storage modulus (∼0.1 MPa) and nominal compression stress (∼22 MPa) are 60 and 2240 times higher than those of pure CNF/PB hydrogel, respectively. The CNF-PPy/PB-3 electrode with a conductivity of 3.65 ± 0.08 S m-1 has a maximum specific capacitance of 236.9 F g-1, and its specific capacitance degradation is less than 14% after 1500 cycles. The CNF-PPy/PB hybrid hydrogels also demonstrate attractive characteristics, including high water content (∼94%), low density (∼1.2 g cm-3), excellent biocompatibility, plasticity, pH sensitivity, and rapid self-healing ability without additional external stimuli. Taken together, the combination of such unique properties endows the newly developed CPHs with potential applications in flexible bioelectronics and provides a practical platform to design multifunctional smart soft materials.

A comparative study of different nanoclay-reinforced cellulose nanofibril biocomposites with enhanced thermal and mechanical properties

Abstract The objective of this research was to comprehensively compare the effects of nanoclay bentonite (BT), halloysite nanotubes (HNTs) and sulfuric acid-etched halloysite nanotubes on the surface wettability, morphological, mechanical and thermal properties of cellulose nanofibril (CNF) biocomposites. A simple and environmental safe casting-evaporation method was used to fabricate these samples, which comprised up to 10 wt% of nanoclay. The surface wettability, tensile testing and TG results showed that the biocomposites with BT exhibited greater hydrophobicity, larger modulus and strength and better thermal stability than with HNTs at low content. However, at high content, the biocomposites with HNTs exhibited larger elongation at break. The DMA results indicated that biocomposites with HNTs exhibited better molecular motion restriction than with BT. These results combined with Fourier Transform Infrared (FTIR) also indicated interfacial interactions between CNF matrix and nanoclay. Acid treatment would help promote the interfacial interactions between HNTs and CNFs, resulting in enhanced mechanical and thermal properties. This comparative study will help in the choice of appropriate nanoclay for use in functional biomaterials in industrial production applications.

Durable superhydrophobic and superoleophilic electrospun nanofibrous membrane for oil-water emulsion separation

Marinepollution andindustrial wastewater have caused serious environmental pollution, thereby resulting into an alarming damage to public health in the past decades, hence the high demand for, cost effective, energy-efficient oil-water separation technologies for the removal of oil contaminants from such water. Herein, we report a facile method to fabricate superhydrophobic/superoleophilic membrane by immersing a polyimide (PI)-based nanofibrous membrane into a water/ethanol/ammonia/dopamine mixture, followed by modification with 1H, 1H, 2H, 2H-perfluorodecanethiol (PFDT). The PI-based membrane exhibited water contact angle (WCA) above 153°, while the oil contact angle (OCA) approached 0°, thereby promoting an outstanding chemical stability which sustained its superhydrophobicity when immersed in aqueous solutions at different pH values. Additionally, the PI-based membrane possesses ultrahigh flux, high separation efficiency and good reusability in oil-water separation. The aforementioned properties, as well as the easily scale-up preparation process ensure that this promising as-fabricated membrane can be applied for practical environmental applications including treatment of oily wastewater and oil spillage clean-up.

Highly efficient visible-light photocatalyst based on cellulose derived carbon nanofiber/BiOBr composites

There is an urgent need to explore alternatives to replace traditional carbonaceous materials because of dwindling oil reserves and increasing atomospheric carbon dioxide. In the present study, the cellulose derived carbon nanofibers (CCNF) were prepared and used to hybridize with bismuth oxybromide to prepare novel photocatalyst composites (CCNF/BiOBr). The structural properties of the prepared composites were then characterized. Afterwards, the photocatalytic performance of the CCNF/BiOBr composites was investigated through degrading rhodamine B (RhB) under continuous visible light irradiation. The results indicated that the pyrolysis process could convert the cellulose to carbon nanofiber with high graphitization degree. The photocatalytic performance of the CCNF/BiOBr composite was better than that of the pure BiOBr, which was ascribed to the introduction of the CCNF into the composite system. The present work provides a promising way to design new photocatalyst composites with desirable carbon alternatives from biomass materials for effective treatment of organic contaminants in water media.Graphical Abstract