How to improve the flame retardancy of lyocell fibers has become an important issue in textile industry. Herein, lyocell fibers were firstly undergone etherification reaction between sodium chloroacetate and the hydroxyl groups of lyocell fibers to obtain carboxymethylated lyocell fibers (CM-lyocell), then the sodium ions of CM-lyocell were replaced by aluminum ions, and the flame retardant lyocell fibers (FR-lyocell) were prepared. Compared with lyocell fibers, the degradation temperature of FR-lyocell decreased by about 80 °C, and the char residue in nitrogen increased from 15.1 to 31.8 wt% at 800 °C. Importantly, the limiting oxygen index (LOI) value of FR-lyocell fabric was increased from 17.2 to 26.4%. Besides, the peak of heat release rate (PHRR) and total heat release (THR) of FR-lyocell had 77.4% and 76.3% reduction, respectively. The FR-lyocell can generate a highly graphitized char layer and release more water at high temperatures, which are beneficial to improving the flame retardancy of lyocell fibers. Moreover, the tensile test showed that the tensile strength of FR-lyocell decreased from 3.95 to 3.08 cN/dtex with a 22% reduction, showing good strength retention.
Graphic abstractIn this paper, we developed a microbial route to fabricate wood-inspired biomimetic composites comparable to natural wood. Focusing on the chemical composition of woody biomass, we performed in situ bioprocessing of bacterial cellulose (BC) imbibed in modified cationic lignin (Catlig), which exhibited significant bioactivity in improving the microbial growth dynamics. The structural and morphological characteristics were enhanced by the formation of hydrophobic and electrostatic interactions between BC and Catlig during biosynthesis. Microbially derived BC/Catlig composites exhibited enhanced thermal stability and crystallinity, with oriented cellulose fibers. The tensile properties, toughness, and specific strength of BC/Catlig composites were comparable to those of a heavy wood species (Zelkova serrata) under hydrated conditions and synthetic soft materials.
Graphic abstractMultifunctional fibers have attracted widespread attention due to applications in flexible smart wearable devices. However, simultaneously obtaining a strong and functional woven fiber is still a great challenge owing to the conflict between the properties mentioned above. Herein, mechanically strong and highly conductive cellulose/carbon nanotube (CNT) composite fibers were spun using an aqueous alkaline/urea solution. The microstructure as well as physical properties of the resulting fibers were characterized via scanning electron microscopy, infrared spectroscopy, mechanical and electrical measurement. We demonstrated that carboxylic CNTs can be well dispersed in alkali/urea aqueous systems which also dissolved cellulose well. The subsequent wet spinning process aligned the CNTs and cellulose molecules inside the regenerated composite fiber well, enhancing the interaction between these two components and endowing the composite fiber having a 20% CNT loading with an excellent mechanical strength of 185 MPa. Benefiting from the formation of conductive paths, the composite fiber with the diameter of about 50 μm possessed an electrical conductivity value in the range of 64–1274 S/m for 5–20 wt% CNT loading. This excellent mechanical strength and high electrical conductivity enable the composite fiber to exhibit a great potential in joule heating; the heating temperature of cellulose/CNT-20 fiber reached more than 55 °C within 15 s at 9 V. In addition, the multifunctional filaments are further manufactured as a water sensor to measure humidity. This work provides a potential material that can be applied in the fields of wearable electronics and smart flexible fabrics.
Graphic abstractThere are growing research interests in flax fibers due to their renewable ‘green’ origin and high strength. However, these natural fibers easily absorb moisture and have poor adhesion with polymer matrix leading to low interfacial strength for the composites. A hybrid chemical treatment technique combining alkali (sodium hydroxide) and silane treatments is adopted in the current study to modify flax fibers for improved performances of flax/polypropylene composites. Changes in chemical composition, microstructure, wettability, surface morphology, crystallinity and tensile properties of single flax fiber before and after chemical treatments were comprehensively characterized using techniques including SEM, FTIR, AFM, XRD, micro-fiber tester, etc. It was found that hemicellulose and lignin at the fiber surface were removed due to alkali treatment, which helped to reduce moisture absorption of the composites. Alkali-treated flax fibers were later subjected to silane treatment, which helped to improve the compatibility between flax fiber and polypropylene matrix. After alkali-silane hybrid chemical treatment, moisture absorption of the composites was further decreased. At the same time, the interfacial bonding strength between flax and polypropylene is significantly enhanced. All these results validate the great advantage of the hybrid chemical treatment approach for flax/polypropylene composites, which has the potential to promote the application of chemical treatment techniques in the plant fiber composite industry.
Graphic abstractThe surgical masks have been essential consumables for public in the COVID-19 pandemic. However, long-time wearing masks will make wearers feel uncomfortable and massive discarded non-biodegradable masks lead to a heavy burden on our environment. In this paper, we adopt degradable chitosan@silver (CS@Ag) core–shell fibers and plant fibers to prepare an eco-friendly mask with excellent thermal comfort, self-sterilization, and antiviral effects. The thermal network of CS@Ag core–shell fibers highly improves the in-plane thermal conductivity of masks, which is 4.45 times higher than that of commercial masks. Because of the electrical conductivity of Ag, the fabricated mask can be electrically heated to warm the wearer in a cold environment and disinfect COVID-19 facilely at room temperature. Meanwhile, the in-situ reduced silver nanoparticles (AgNPs) endow the mask with superior antibacterial properties. Therefore, this mask shows a great potential to address the urgent need for a thermally comfortable, antibacterial, antiviral, and eco-friendly mask.
Graphical abstractVulcanized fibers are all-cellulose materials made from cotton and/or wood cellulose after aqueous zinc chloride treatment. These materials were invented in the UK in the mid-nineteenth century and is widely used because of their excellent characteristics, such as impact resistance and electrical insulation. Recently the matured vulcanized fibers have been recognized as renewable and biodegradable materials and reevaluated with advanced cellulose technologies derived from cellulose nanofibers (CNFs) and all-cellulose composites. The microscopic analysis based on the improved freeze-drying method revealed that the strength of vulcanized fiber sheets can be attributed to the chemically defibrillated CNFs. The architecture is similar to all-cellulose composites made from the same raw materials in which the residual cellulose fibers serve as reinforcement, and the CNFs serve as adhesives or matrix components. In this report, we describe the history and structural characteristics of vulcanized fibers and introduce a new aspect in aqueous zinc chloride treatment of cellulose.
Graphical abstractCellulose nanocrystals (CNCs) with high crystallinity exhibit high mechanical stiffness and strength. However, the high dispersibility of CNCs results in limited spinnability and orientation. In this study, oxidized nanocellulose was selected to obtain regionally oxidized CNCs (RO-CNC) with carboxyl groups appended. For the formation of orientable and extensible RO-CNC filaments, chitosan was introduced as the sheath solution to induce orientation by electrostatic action. The chemical structures were analyzed by Fourier transform infrared spectroscopy. The morphology of the oriented CNCs filaments was characterized by scanning electron microscopy and wide-angle X-ray scattering. Analysis of the relationship between the mechanical strength and the CNCs directional arrangement revealed that the mechanical strength of the composite fibers increased with the injection speed ratio as a result of the orientation of the RO-CNC. The mechanical strength of the oriented reinforced composite filaments reached as high as 104 MPa with an orientation index of 0.73. The tensile strength and elastic modulus of the filaments increased by 33% and 20%, respectively, compared to the unmodified CNCs spun fiber.
Graphic abstractCellulose nanofibril (CNF) aerogels have attracted great interests in recent years due to the low cost, sustainability and biocompatibility of raw CNF. However, the poor thermal stability and flammable feature of CNF aerogels have limited their wider applications. In this paper, polydopamine/CNF composite aerogels with good comprehensive properties are fabricated by modification of CNF with polydopamine and metal coordination bonds crosslinking. The microstructure and properties of composite aerogels are thoroughly characterized by a variety of tests. It is found that the microstructure of aerogels are more regular and the compressive strength of aerogels are enhanced by the incorporation of polydopamine and Fe3+ crosslinking. Importantly, the thermal stability and flame resistance of aerogels are significantly improved, which permit the application of composite aerogels in high-temperature thermal insulation. In addition, the reversible characteristic of metal coordination bonds allows the water induced healing of fractured composite aerogels. This study is expected to provide information for future development of green and high-performance aerogels.
Graphic abstractThis study introduces an effective route to fabricate chitosan (CS)-based film. The films were prepared through cross-linking reaction between CS and hydroxyethyl cellulose (HEC) using epichlorohydrin (ECH) as the cross-linker and simultaneously in-situ loading with CuO nanoparticles. FT-IR and loading efficiency results indicated the occurrence of inter- and intra-molecular cross-linking reaction between CS and HEC. XRD and EDS analyses showed that the CuO nanoparticles were evenly deposited onto CS film matrixes. SEM characterization showed that the films were of compact, dense and uniform cross morphologies, as well as obvious voids. The films also exhibited desired swelling ratio and water vapor permeability. The enhanced tensile strength was obtained with a maximum value of 77.02?±?3.26 MPa, while the stretch-ability slightly decreased. The thermal stability of the films decreased after cross-linking with HEC. The antibacterial ability of the films was generally improved with the increase of HEC and ECH contents.
Graphical abstractPreparation and properties of epichlorohydrin-cross-linked chitosan/hydroxyethyl cellulose based CuO nanocomposite films
Adsorbents that exhibit a high adsorption capacity and facile recyclability are considered promising materials for dye wastewater remediation. In this work, a novel sulfonate-decorated cotton fiber was fabricated as a recyclable adsorbent for the highly efficient removal of cationic dyes. Herein, poly(sodium p-styrene sulfonate-co–N-methylol acrylamide) (P(SSNa-co-NMAM)) with SSNa units as adsorption sites and NMAM units as thermal-crosslinking points was synthesized for the modification of cotton fibers. As expected, the as-obtained P(SSNa-co-NMAM)-coated cotton fibers (PCFs) presented outstanding adsorption capacities toward cationic dyes, even in the simulated effluents. The processes of cationic dye absorbing onto the PCFs were well fitted by the Langmuir isotherm model and pseudo-second-order kinetics. The thermodynamic study revealed that the adsorption reaction of the cationic dyes onto PCF was spontaneous, and the efficiency of adsorption was more desirable at higher temperatures. The maximum adsorption capacities of PCF toward methylene blue (MEB), rhodamine B (RhB), and malachite green (MG) were 3976.10, 2879.80, and 3071.55 mg/g, respectively. The dye removal mechanism was ascribed predominantly to electrostatic interactions. Moreover, the adsorption capacity of the PCFs toward cationic dyes was slightly influenced by the pH of the solutions because of the sulfonate moieties, which exhibit stability under acidic and alkaline conditions. Furthermore, the recyclability and reusability of the as-prepared PCFs were satisfactory and good mechanical properties and thermal stability were observed compared to those of pristine cotton fibers. Given the aforementioned results, the as-obtained PCFs are highly promising as ideal adsorbents for the remediation of dye-contaminated wastewater.
Graphical abstractThe dry pulp direct kneading method is an industrially viable, low-energy process for manufacturing cellulose nanofiber (CNF)-reinforced polymer composites, where the chemically modified pulps are nanofibrillated and uniformly dispersed in the polymer matrix during melt compounding. In the present study, cellulose fibers of various sizes ranging from surface-fibrillated pulps (20 μm in width) to fine CNFs (20 nm in width) were prepared from softwood bleached kraft pulps using a refiner and a high-pressure homogenizer. These cellulose fibers were modified with alkenyl succinic anhydride and dried. The dried fibers were used as a feed material for melt compounding in the dry pulp direct kneading method to fabricate CNF-reinforced high-density polyethylene (HDPE). When surface-fibrillated pulps were employed as a feed material, the pulps were nanofibrillated and dispersed uniformly in the HDPE matrix during melt compounding. The resulting composites had much better properties—i.e., much higher tensile modulus and strength values, and much lower coefficient of thermal expansion values—than the composites produced using pulps without pre-fibrillation. However, when CNFs were used as a feed material, they were shortened and agglomerated during melt compounding, and the properties of the composites consequently deteriorated. The study concludes that surface-fibrillated pulp, which can be produced cost-effectively using a refiner on an industrial scale, is more suitable as a feed material than CNFs for melt compounding in the dry pulp direct kneading method. This finding enables the elimination of a preliminary step in the preparation of CNFs from pulps, which is a time-consuming and energy-intensive process.
Graphical abstractHerein, cellulose nanofibrils (CNF), alkali lignin (AL), and montmorillonite (MMT) were used to produce reinforced polyvinyl alcohol (PVA) hydrogels. The effects of MMT and AL contents on the rheological properties of reinforced hydrogel were studied. Compared with PVA/CNF hydrogel, the storage modulus of 40 wt% MMT-reinforced PVA hydrogel was increased by 41.4%. The rheological properties of MMT-enhanced PVA hydrogel could be adjusted by the variation of MMT loading. Also, as the PVA matrix had a synergistic effect with the embedded MMT and AL, the composite hydrogel demonstrated high efficiency in the removal of methylene blue dye (MB) from wastewater. Adsorption tests conducted at various time intervals (60–360 min) show that the hydrogels containing same content of MMT had higher removal efficiency. The MB adsorption of PVA/2CNF-0Li-40MMT was over 98.0%, whereas its adsorption equilibrium time and maximum adsorption capacity (qm) were 360 min and 67.2 mg/g, respectively. However, an extremely high content of MMT reduced the MB adsorption rate.
Graphic abstractIncreasing electromagnetic pollution calls for electromagnetic interference (EMI) shielding materials, especially sustainable, lightweight, and environmentally stable, biomass-based materials. MXene-coated wood (M/wood) is prepared by simply spraying MXene sheets on the wood surface. Varying this spray coating manipulates the shielding performance and its application to different wood species. The M/wood exhibits high electrical conductivity (sheet resistance is only 0.65 Ω/sq) with an excellent EMI shielding effectiveness of 31.1 dB at 8.2?~?12.4 GHz and is also fire retardant. Furthermore, waterborne acrylic resin (WA) is coated on M/wood to enhance environmental stability. The WA coating improves EMI shielding performance stability after water-soaking and drying testing and prevents the peeling of MXene from wood. These satisfactory properties of WA-M/wood and the facile manufacturing approach promote the feasibility of wood-based EMI shielding materials.
Graphical abstractExploitation of cotton fabric as electromagnetic interference (EMI) shielding substrates have attracted a growing interest due to their desirable low carbon footprint, economic feasibility, and sustainability. Herein, a facile strategy was proposed for preparing a cellulose-based multifunctional PNIPAAm/PPy hydrogel/cotton (PPHC) EMI shielding composites with simultaneous high-efficient electro-photo-thermal conversion and comfort regulation functions. The PPHC was fabricated via in situ polymerization conductive PPy hydrogel on cotton substrate followed by deposition of PNIPAAm. Benefiting from the unique interconnected three-dimensional networked conductive structure of PPy hydrogel, the obtained PPHC composites exhibited high conductivity (15 mS/cm), and EMI shielding effectiveness (EMI SE?~?40 dB) in the frequency of 8.2–12.3 GHz. Moreover, the PNIPAAm coating endowed the composite fabrics with adjustable wettability performance in response to external temperature, leading to excellent comfort regulation performance. This work provided feasible avenue toward low cost and sustainability cotton-based EMI shielding composites with efficient EMI shielding and comfort regulation performance.
Graphical abstractTo obtain high performance of nanocomposite films made of cellulose nanofibrils (CNFs) and montmorillonites (MMTs), highly ordered nanostructures and abundant interfacial interactions are of extreme importance, especially for CNF film with high MMT content. Here, we tend to unveil the influence of exfoliation degree of MMTs and their interfacial interactions with CNFs on the properties of ensuing nanocomposite films. Monolayer MMTs (ML-MMTs) prefer to form highly ordered nanostructure during water evaporation induced self-assembly. The obtained nanocomposite film with 30 wt% ML-MMTs exhibits a tensile strength of 132 MPa, a total light transmittance of 90.2% (550 nm), and water vapor transmission rate (WVTR) of 41.5 g mm/m2 day, better than the film made of original MMTs (O-MMTs) and CNFs (30 MPa strength, 60% transparency, and 78.7 g mm/m2 day WVTR). Moreover, the physical properties (153 MPa strength and 20.9 g mm/m2 day WVTR) of nanocomposite film can be further enhanced by constructing ionic interactions between the ML-MMT and CNF using 0.5 wt% cationic polyethylenimine (PEI). However, as the amount of PEI continues to increase, its performance will be deteriorated dramatically because of the disordered orientation of ML-MMTs. This work could provide an insight into the fabrication of high performance MMT/CNF nanocomposite film for advanced applications.
Graphical abstractOceans and soils have been contaminated with traditional plastic due to its lack of degradability. Therefore, green biopolymer composites reinforced with cellulose nanocrystal-zinc oxide hybrids (ZnO hybrids) with good biodegradation ability provided a positive impact on reducing environmental challenges. In this work, the effect of various morphologies of ZnO hybrids on the biodegradation ability of poly(butylene adipate-co-terephthalate), PBAT) under seawater, soil burial, and UV aging conditions were investigated. Sheet-like ZnO hybrids (s-ZnO hybrid) efficiently enhanced the mechanical, UV-blocking properties and biodegradation ability of PBAT nanocomposite films. Compared to neat PBAT, the best tensile strength of PBAT nanocomposite with 2 wt% s-ZnO hybrid was increased by 15.1%, meanwhile this nanocomposite films showed the highest biodegradation rate after 80 days of soil degradation and 90 days of seawater degradation. Besides, three possible biodegradation mechanisms of green PBAT nanocomposite films were presented, hinting that such PBAT nanocomposite have great promising packaging applications.
Graphic abstractIn this study, the effect of pectin extraction method on the properties of cellulose nanofibers (CNFs) isolated from sugar beet pulp (SBP) was studied. Pectin was extracted by the industrially practiced method by sulfuric acid hydrolysis or by enzymatic hydrolysis using a cellulase/xylanase enzymes mixture. The CNFs were then isolated by high-pressure homogenization and investigated in terms of their chemical composition, crystallinity, size, degree of polymerization, and re-dispersion in water after freeze-drying. The mechanical properties and surface characteristics of CNF films were also studied. The results showed that fibrillation of the de-pectinated SBP was more efficient for the acid hydrolyzed SBP. CNFs from the acid-hydrolyzed SBP had a slightly wider diameter, higher crystallinity, viscosity, and α-cellulose content but a lower degree of polymerization than CNFs from the enzyme-hydrolyzed SBP. Owing to the presence of more residual hemicelluloses in the CNFs from the enzyme-hydrolyzed SBP, the CNFs had higher re-dispersion ability in water. CNF films from enzyme-hydrolyzed SBP displayed slightly better mechanical properties and higher water contact angle than acid-hydrolyzed CNF films.
Graphic abstractFabricating mechanically strong hydrogels that can withstand the conditions in internal tissues is a challenging task. We have designed hydrogels based on multicomponent systems by combining chitosan, starch/cellulose, PVA, and PEDOT:PSS via one-pot synthesis. The starch-based hydrogels were homogeneous, while the cellulose-based hydrogels showed the presence of cellulose micro- and nanofibers. The cellulose-based hydrogels demonstrated a swelling ratio between 121 and 156%, while the starch-based hydrogels showed higher values, from 234 to 280%. Tensile tests indicated that the presence of starch in the hydrogels provided high flexibility (strain at break?>?300%), while combination with cellulose led to the formation of stiffer hydrogels (elastic moduli 3.9–6.6 MPa). The ultimate tensile strength for both types of hydrogels was similar (2.8–3.9 MPa). The adhesion and growth of human osteoblast-like SAOS-2 cells was higher on hydrogels with cellulose than on hydrogels with starch, and was higher on hydrogels with PEDOT:PSS than on hydrogels without this polymer. The metabolic activity of cells cultivated for 3 days in the hydrogel infusions indicated that no acutely toxic compounds were released. This is promising for further possible applications of these hydrogels in tissue engineering or in wound dressings.
Graphical abstractMembrane applications for the separation of surfactant-stabilized emulsions are often constrained by a deficiency in permeability and anti-fouling properties. Herein, special wetted cotton fabric with a protective layer (P-MH@CF) for durable anti-fouling performance was synthesized by a two-step method, which was related to interfacial ion migration technology and unilateral spraying treatment. Permeability of water and separation performance of P-MH@CF membrane were investigated systematically. Emulsions stabilized by anionic, cationic, or non-ionic surfactant were successfully separated with high efficiency. In the process of separation, the oil droplets surrounded by surfactants were difficult to demulsify and gathered physically on the membrane surface to form a “cream layer”. The stearic acid acted as a protective layer, like a quilt, protecting the membrane from contamination. The membrane retained robust reusability for separation even after the “cream layer” had been washed off, which was promising for the remediation of oily wastewater containing surfactants.
Graphical abstractSurface modification of fabrics is a powerful strategy that can endow fabrics with desired effects while keeping the intrinsic properties. Herein, an ordinary strategy, dipping-drying based layer-by-layer self-assembly (LbL) coating, is reported to functionalize fabrics’ surfaces. Firstly, the novel cation waterborne polyurethanes (QAHDPU) and anion waterborne polyurethanes (HDPU) are successfully designed and synthesized. By incorporating targeted molecule, hydantoin diol (HD) and quaternary ammonium salt with long alkyl chain (DOQA), the QAHDPU are antibacterial and hydrophobically functionalized. Taking advantage of strong adhesion, waterborne polyurethanes (WPUs) are physically bonded to surfaces of fabrics to generate durable antibacterial and hydrophobic fabrics. The QAHDPU with long alkyl chain combined with rough and porous fabric surface fabricates hydrophobic fabric surface, which can prevent bacteria from adhering to the fabrics. Furthermore, the coated fabrics present excellent antibacterial properties after chlorination, forming a second barrier against bacteria. The chlorinated coated fabrics, can inactivate 85.0–99.9% of Staphylococcus aureus and 85.0–97.7% of Escherichia coli with contact time of 60 min. The hydrophobic properties of coated fabrics are greatly improved with water contact angles of 122.0°–141.1°. In addition, the proposed method is applicable for a variety of fibers and expected to be used for industrial production.
Graphical abstract