Vulcanized 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 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 review is the first part of a comprehensive review of hydrophobisation of lignocellulosic materials. The purpose of this review has been to compare physical hydrophobisation methods of lignocellulosic materials. We have compared molecular physical adsorption with plasma etching and grafting. Adsorption methods are facile and rely upon the simple mixing or coating of the substrate with the hydrophobing agent. However, none of the surfactant-based methods reviewed here reach contact angles above 90°, making them unsuitable for applications where a high degree of hydrophobisation is required. Nevertheless, surfactant based methods are well suited for compatibilising the lignocellulosic material with a hydrophobic matrix/polymer in cases where only a slight decrease in the hydrophilicity of the lignocellulosic substrate is required. On the other hand, wax- and lignin-based coatings can provide high hydrophobicity to the substrates. Plasma etching requires a more complex set-up but is relatively cheap. By physically etching the surface with or without the deposition of a hydrophobic coating, the material is rendered hydrophobic, reaching contact angles well above 120°. A major drawback of this method is the need for a plasma etching set-up, and some researchers co-deposit fluorine-based layers, which have a negative environmental impact. An alternative is plasma grafting, where single molecules are grafted on, initiated by radicals formed in the plasma. This method also requires a plasma set-up, but the vast majority of hydrophobic species can be grafted on. Examples include fatty acids, silanes and alkanes. Contact angles well above 110° are achieved by this method, and both fluorine and non-toxic species may be used for grafting.
Graphical 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
The development of a simple surface barrier discharge plasma device is presented to enable more widespread access to and utilization of plasma technology. The application of the plasma device was demonstrated for pretreatment of wood prior to application of protective coatings for outdoor usage. The coatings' overall performance was increased, showing a reduction or absence of cracking due to weathering on plasma-pretreated specimens. Moreover, after ten months of outdoor weathering, the plasma-pretreated specimens showed fewer infections with biotic factors and improved adhesion performance in cross-cut tests, while the surface gloss performed independently from plasma pretreatment. In contrast to that, plasma-pretreated specimens were slightly more prone to discoloration due to outdoor weathering, whereas the plasma pretreatment did not impact the initial color after coating application.
Graphic abstractIonic cellulose nanocrystals (CNCs) are interesting surface-active particles for encapsulating a lipophilic liquid in water. A CNC is modified chemically to a negative charge (an S-CNC) by surface treatment with sulfuric acid. Despite the amphiphilic nature of S-CNCs, it is difficult to determine the degree of substitution for emulsification of lipophilic liquids, especially when the surface energy is low and polarity is high. Here, we control the substitution of S-CNCs by desulfation of S-CNCs (dS-CNCs) using a low-concentration hydrochloric acid solution. Decreased surface charge of S-CNCs was expected, and the lipophilic affinity of dS-CNCs increased compared with those of S-CNCs. Six oils with differing surface tensions were selected for determination of the effect of charged CNCs on emulsification. The stability of the emulsion was evaluated by emulsion fraction, emulsion particle size, and surface tension of emulsified solutions from dS-CNCs and oils.
Graphical 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 abstractThe development of a versatile platform that can separate oil/water mixture, remove dye from water, and purify wastewater is extremely desirable, yet still hard to realize. Herein, to address this challenge, a composite hydrogel was produced by freezing–thawing treatment using chitosan, polyvinyl alcohol, and carbon black as the raw materials. The obtained hydrogel displayed both slippery oil-repellency and water-affinity in air, underwater, when submerged in oil, and exploiting this special wettability, the hydrogel coated mesh can be used to separate oil/water mixtures efficiently. After 25 oil–water separation cycles, the hydrogel-coated filter still had a separation efficiency of over 98%. With its superhydrophilicity and active functional groups, the resulting hydrogel was able to absorb dye molecules dissolved in water effectively. Due to the photothermal effect of carbon black, the local temperature of the hydrogel was increasing quickly under sunlight illustration, which allowed it to be an advanced platform for daily wastewater purification through solar distillation.
Graphical abstractA versatile hydrogel platform for oil–water separation, dye adsorption, and domestic wastewater purification was developed.
Oceans 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 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 abstractMultifunctional materials for water purification have attracted significant attention due to the increased water pollution problems. However, fabricating the low-cost, effective, and recyclable separation material for wastewater containing various hazardous substances is still a challenge. Herein, we developed an Ag/TiO2@PDMS coated cotton fabric with self-cleaning ability, high flux, superior visible-light photocatalytic ability, and recyclability via the “powder?+?glue” strategy. The composites are superhydrophobic (water contact angle 157°) and show high separation efficiency. After 20 times of repeated use, the separation efficiency remains 16,322 Lm?2 h?1, and methylene blue (MB) 's degradation rate remains almost unchanged. The high oil purification, catalytic property, excellent stability in harsh conditions, and recyclability enable the material as a satisfactory candidate for water purification.
Graphical abstractMillions of tons of fruit waste are generated globally every year from agricultural residues, which makes it essential to find alternative uses to increase their aggregate value and reduce their environmental impact. The present study aimed to explore pineapple peel as an alternative source of cellulose by evaluating its chemical composition and physical properties, which are essential for applications. A sequence of chlorine-free treatments was applied to purify the cellulose by removing noncellulosic components in the fresh pineapple peels. The cellulosic pulp was characterized regarding its chemical composition and characterized by Nuclear Magnetic Resonance (13C NMR), X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis to determine crystallinity, structural properties, morphology, and thermal characteristics, respectively. The results revealed that the pineapple peel amorphous segments containing hemicelluloses and lignin were extensively removed with increasing chemical treatment steps, leading to increased purity, crystallinity index, and thermal stability of the extracted cellulose pulps. The maximum thermal degradation (150 °C) and crystallinity index (80.9%) were determined for the cellulosic material obtained from the second bleaching (2B) step. The cellulose content increased from 24% in the starting material (fresh pineapple peel) to 80.9% in the bleached cellulose (2B). These results indicate that the extracted cellulose from pineapple peel has characteristic for applications such as the production of cellulose nanocrystals due to the high crystallinity.
Graphical abstractUniformly-sized porous cellulose beads functionalized with amidoxime groups were prepared for the first time using a microfluidic method with N-methylmorpholine N-oxide (NMMO) monohydrate as a cellulose solvent. The molten state cellulose dope in NMMO monohydrate (cell/NMMO dope) as a disperse phase and hot mineral oil as a continuous phase were used in a T-junction microfluidic chip to produce uniformly-sized cell/NMMO droplets. Coagulation of the molten state cell/NMMO droplet at high temperature and amidoxime functionalization could prepare the highly-porous spherical amidoxime-functionalized cellulose beads with a uniform fibrous open internal structure. The prepared amidoxime-functionalized cellulose beads showed excellent metal adsorption properties with a maximum adsorption capacity of?~?80 mg g?1 in the case of Cu2+/phthalate ions. The newly developed highly-porous cellulose beads can open many new applications with other proper functionalization at the reactive hydroxyl groups of the cellulose.
Graphic abstractCellulose-based matrices are expected to be ideal enzyme carriers due to their sustainability and biocompatibility. However, the linkages between immobilized enzymes and celluloses often suffer from low-density and non-biodegradability, leading to inefficient loading of enzymes as well as persistent generation of solid wastes after reuse. In the present study, cellulose-based functional materials with degradable polycarbonates brushes have been successfully synthesized as enzyme carriers via ring-opening polymerization of 5-methyl-5-allyloxycarbonyl-1,3-dioxan-2-one (MAC) following with ally epoxidation of MAC units. After covalent bonding with laccase, the resulting HPC-PMAC-Laccase could assemble in aqueous solution to form spherical nanoparticles with an enzyme immobilization efficiency of 88%. The immobilized laccase showed more tolerance towards pH and high temperature compared with free laccase. Moreover, the immobilized laccase demonstrated effective removal efficiency of bisphenol A and reached 83% in 3 h. After repeated usage for 8 times, the HPC-PMAC-Laccase still maintained relatively high enzyme activity. Especially, the polycarbonates brushes in the enzyme carriers could be totally hydrolyzed in 12 h to achieve its degradable property.
Graphical abstractCellulose-based functional polycarbonates as degradable enzyme carriers.
This study prepared a waterproof cellulose nanofibril (CNF) sheet via the deposition of an alkyl ketene dimer (AKD) on the sheet’s controlled porous structure. The porosity of the CNF sheet was controlled by drying under different conditions, which included hot-press drying (HD) and solvent-exchange drying (SD), and the effect on the hydrophobization and water-related barrier performance of the sheet were investigated. When the SD sheet was immersed in an AKD wax solution, the sheet exhibited super-hydrophobicity and a lower water vapor transmission rate, compared with the HD sheet. This indicated that the porous structure of the SD sheet enabled AKD to be adsorbed on both the surface and the inner surface and it filled in the pores of the sheet, thereby giving rise to excellent waterproofing properties. The performance of a hydrophobized SD sheet as a water barrier material was comparable to a linear low-density polyethylene film. This study confirms the possibility for AKD wax to be immersed in a porous CNF sheet and used as a potential barrier material in hydrogel packaging.
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 abstractDevelopment of self-sanitizing cellulose and cellulose paper-based products will increase human safety and hygiene. In the present work, a softwood bleached kraft pulp (SBKP) was oxidized by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation in water at pH 10 at two NaClO addition levels (3 and 5 mmol g?1 based on the dry weight of SBKP). The fibrous TEMPO-oxidized SBKPs (TO-SBKPs) were subsequently incorporated with silver nanoparticles (AgNPs) by soaking in aqueous silver nitrate (AgNO3) solution and subsequent thermal reduction. The C=O absorption band in FTIR spectra of AgNP-containing TO-SBKPs increased with increasing Ag content, showing that the C2/C3 hydroxy groups in TO-SBKPs were oxidized to ketones by reduction of Ag+ ions to AgNPs during heating at 100 °C for 1 h. Scanning electron microscopy images showed that the AgNPs were almost homogenously distributed on the surface of each TO-SBKP fiber with an average diameter of 32–40 nm regardless of different Ag contents. Handsheets were prepared from SBKP and the AgNP-containing TO-SBKP at various weight ratios. The handsheets showed sufficient antimicrobial activities against a Gram-negative Escherichia coli strain and a Gram-positive Staphylococcus aureus strain. The tensile strength of the handsheets was significantly improved by mixing the AgNP-containing TO-SBKP with SBKP. The 20% TO-SBKP/Ag-containing SBKP sheets were optimal in terms of efficient antimicrobial activities and good mechanical properties. Thus, the AgNP-containing TO-SBKP sheets have potential for use as antimicrobial paper and related packaging materials produced using the conventional papermaking process.
Graphic abstractThe present work aims to investigate the feasibility of oxalic acid-choline chloride deep eutectic solvent (OA-ChCl DES), which serves as a promising green solvent that utilized in the acidic deep eutectic solvent (DES) hydrolysis. Oxalic acid-choline chloride DES cellulose nanocrystal (OA-ChCl DES CNC) was isolated from the bleached DES treated pulp (BP) through the acidic DES hydrolysis using 1:1 molar ratio of OA-ChCl DES. The functional groups, crystallinity index, morphological structure, particle size, zeta potential, thermal stability and surface chemistry of the OA-ChCl DES CNC were compared with the sulphuric acid cellulose nanocrystal (SA-CNC) that prepared via sulphuric acid hydrolysis. The findings revealed the presence of negatively charged carboxyl groups on OA-ChCl DES CNC surface after the acidic DES hydrolysis. The physicochemical analyses verified that the OA-ChCl DES CNC was in nano-sized range with polydispersity index (PdI) of 0.56, indicating slightly monodispersed nanoparticles. A stable OA-ChCl DES CNC colloidal suspension with zeta potential value of ?52.1?±?5.2 mV was obtained. The OA-ChCl DES CNC outweighed the SA-CNC in term of thermal stability (288 °C) despite having a slightly lower crystallinity index (76.7%). In fact, the OA-ChCl DES CNC with a yield of 55.1% was achieved through the acidic DES hydrolysis, suggesting that the OA-ChCl DES was capable of promoting efficient cleavage of strong hydrogen bonds in BP.
Graphic abstractCaesalpinia sappan L. wood fiber (CSWF), a novel advanced bio-reinforcement for polybutylene succinate (PBS) composite films, has shown significant promise ranging from 0 to 15 part per hundred of resin (phr). The functional groups and interactions, morphology, thermal stability, mechanical characteristics, and biodegradability were all investigated. Without treatment or any compatibilizers, CSWF could be well-dispersed in the PBS matrix. The PBS/CSWF10 composite film had highest mechanical strength, with a tensile strength of 12.21 N/mm2 and a break elongation of 21.01%. Biodegradability studies indicated that the PBS/CSWF10 composite films degraded completely in three months. Furthermore, the Ea of degradation resulting from TGA and the shift of wavenumber resulting from FTIR revealed that the addition of CSWF has a greater interaction between additive and martix than conventional cellulose. The PBS/CSWF10 composite has the potential to be environmentally friendly, with promising short-term degradation and rising mechanical characteristics. Therefore, it is the optimum concentration of a certain biocomposite film. As a result, a novel advanced natural-based cellulose for biopolymer composites film was discovered, as well as other benefits for bio-reinforcement of the green plastic composite film industry.
Graphical abstractHow 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 abstract