Yu Xue

Traditional handmade bamboo paper is a commonly used material for the restoration of ancient books and the printing of classic texts. This study discussed the ageing behavior of handmade bamboo paper under dry thermal ageing conditions. The filter paper composed of cellulose serves as a reference example. The results showed that the mechanical properties of bamboo paper containing lignin remained stable for a certain period of time before declining when the pH was less than 7. While the mechanical properties of the filter paper immediately decreased when the pH falls below 7.0. Pore structure analysis indicated that bamboo paper undergoes substantial structural changes in the early stages of aging, with an increase in specific surface area and pore volume, and a decrease in average pore size. These changes then stabilize over time. This may be attributed to the fact that hemicellulose and lignin help maintain the overall integrity of the bamboo paper fibers.The study provides a scientific basis for understanding bamboo paper ageing mechanisms and offers references for preserving historical documents.

Lignin, the most abundant natural aromatic polymer, holds considerable promise for applications in various industries. The primary obstacle to the valorization of lignin into useful materials is its low molecular weight and diminished chemical reactivity, attributable to its intricate structure. This study aimed to treat lignocellulosic biomass using a switchable solvent (DBU–HexOH/H₂O) derived from the non-nucleophilic superbase 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU), which efficiently separates and extracts lignin from poplar wood. Additionally, it sought to characterize fundamental properties of the extracted switchable solvent lignin (SSL) and propose a mechanism for its separation. In comparison to milled wood lignin, SSL exhibits a greater molecular weight, superior homogeneity, and enhanced stability. The SSL sample was analyzed using spectroscopies including infrared spectroscopy, nuclear magnetic resonance, and X-ray photoelectron spectroscopy. The findings indicated that the structure of SSL was preserved, with the switchable solvent primarily cleaving the C–C and α-O-4 bonds, resulting in a low hydroxyl content, an elevated H/C ratio, and a reduced O/C ratio. The SSL was successfully prepared to lignin nanoparticles (LNPs) with size range of 531–955 nm. This paper presents a technique for processing lignocellulosic biomass using a switchable solvent, highlighting advancements in lignin’s structure and enhancing its use in the chemical sector.

Handmade papers, as carriers of paper-based cultural relics, have played a crucial role in the development of human culture, knowledge, and civilization. Understanding the intricate relationship between the structural properties and degradation mechanisms of handmade papers is essential for the conservation of historical documents. In this work, an artificial dry-heat-accelerated aging method was used to investigate the interplay among the mechanical properties of paper, the degree of polymerization (DP) of cellulose, the chemical composition, the hydrogen bond strength, the crystallinity, and the degree of hornification for paper fibers. The results demonstrated for the first time that the mechanical properties of handmade bamboo paper exhibited an initial plateau region, a rapid decline region, and sometimes a second plateau region as it undergoes a dry-heat aging process. The changes in cellulose, hemicellulose, and lignin content were tracked throughout these three stages. The lignin content was relatively stable, while the cellulose and hemicellulose content decreased, which was consistent with the observed decline in mechanical properties. When the DP of cellulose decreased to the range of 600–400, there was a critical point in the mechanical properties of the paper, marking a transition from the initial stable region to a rapid decline region. The fiber embrittlement caused by cellulose chain breakage resulting from the decrease in DP was counteracted by the enhancement of intermolecular hydrogen bonds and the hornification process. A second stable region appeared when the DP was less than 400, marking a transition from a balanced or slightly decreasing trend in the initial plateau region to a sharp decline. This study also discussed for the first time that the formation of the second plateau region may be due to the presence of hemicellulose and lignin, which hinder the further aggregation of cellulose and maintain the structural stability of the fiber cell. The findings of this study can provide guidance for improving ancient book preservation strategies. On the one hand, understanding how these components affect the durability of paper can help us better predict and slow down the aging of ancient books. On the other hand, specific chemical treatment methods can be designed to stabilize these components and reduce their degradation rate under adverse environmental conditions.

Handmade papers, as carriers of paper-based cultural relics, have played a crucial role in the development of human culture, knowledge, and civilization. Understanding the intricate relationship between the structural properties and degradation mechanisms of handmade papers is essential for the conservation of historical documents. In this work, an artificial dry-heat accelerated ageing method was used to investigate the interplay between the mechanical properties of paper, the degree of polymerization (DP) of cellulose, chemical composition, hydrogen bond strength, crystallinity, and degree of hornification. The results show that the mechanical properties of handmade bamboo paper exhibited a first plateau region, a rapid decline region, and sometimes a second plateau region. A critical point in the mechanical properties of the paper occurs when the cellulose DP decreases to a range of 400-600, signifying a shift from the initial plateau to a sharp decline phase. The strengthening of intermolecular hydrogen bonds and the hornification process help counteract the embrittlement of fibers caused by cellulose chain scission due to DP reduction. A secondary plateau emerges when the DP is smaller than 400, cellulose degradation is slow, and the component content, hydrogen bond strength, crystallinity, and degree of hornification reach a secondary plateau.

Deep eutectic solvents (DESs) are promising for lignin dissolution and extraction. However, they usually possess high polarity and are difficult to recycle. To overcome this drawback, a variety of switchable ionic liquids (SILs) composed of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and alcohols was synthesized and screened. According to the thermodynamic modeling suggestions, the selected DBU–HexOH SIL was coupled with hydrogen-bond donors to form switchable-DES (SDES) systems with moderated viscosity, conductivity, and pH while maintaining switchability. The SDESs produced a well-improved lignin and lignin model compound solubility compared with those of SILs; charging CO₂ into SDES (SDES_CO2) caused a further increase in solubility. The solubility (25 °C) of syringic acid, ferulic acid, and milled wood lignin in SDES_CO2 reached 230.57, 452.17, and 279.12 mg/g, respectively. Such SDES-dissolved lignin can be regenerated using acetone as an anti-solvent. The SDES-regenerated lignin exhibited a well-preserved structure with no noticeable chemical modifications. Furthermore, the SDES_CO2 lignin possessed a higher molecular weight (Mw = 10,340 g/mol; Mn = 7672 g/mol), improved uniformity (polydispersity index = 1.35), and a higher guaiacyl lignin unit content compared with the original milled wood lignin. The SDES system proposed in the present work could benefit the fractionation of lignin compounds and facilitate downstream industrial processes.

Hydrogels have attracted much attraction for promising flexible electronics due to the versatile tunability of the properties. However, there is still a big obstacle to balance between the multi-properties and performance of wearable electronics. Herein, we propose a salt-percolated nanocellulose composite hydrogel which was fabricated via radical polymerization with acrylic acid as polymer networks (NaCl-CNCs-PAA). CNCs were utilized as a reinforcing agent to enhance the mechanical properties of the hydrogel. Moreover, the abundant hydroxyl groups endow the hydrogel with noncovalent interactions, such as hydrogen bonding, and the robustness of the hydrogel was thus improved. NaCl incorporation induced the electrostatic interaction between CNCs and PAA polymer blocks, thus facilitating the improvement of the stretchability of the hydrogel. The as-obtained hydrogel exhibited excellent stretchability, ionic conductivity, mechanical robustness and anti-freezing properties, making it suitable for self-powered sensing applications. A single-mode triboelectric nanogenerator (C-TENG) was fabricated by utilizing the composite hydrogel as electrodes. This C-TENG could effectively convert biomechanical energy to electricity (89.2 V, 1.8 µA, 32.1 nC, and the max power density of 60.8 mW m⁻² at 1.5 Hz.) Moreover, the composite hydrogel was applied for strain sensing to detect human motions. The nanocellulose composite hydrogel can achieve the application as a power supply in integrated sensing systems and as a strain sensor for human motion detection.

To improve the physical strength of regenerated cellulose fibers, cellulose dissolution was analyzed with a conductor-like screening model for real solvents in which 1-allyl-3-methylimidazolium chloride (AMIMCl) worked only as a hydrogen bond acceptor while dissolving the cellulose. This process could be promoted by the addition of urea, glycerol, and choline chloride. The dissolution and regeneration of cellulose was achieved through dry-jet and wet-spinning. The results demonstrated that the addition of hydrogen bond donors and acceptors either on their own or in combination can enhance the tensile strength, but their effects on the crystallinity of the regenerated fibers were quite limited. Compared with the regenerated fibers without any additives, the tensile strength was improved from 54.43 MPa to 139.62 MPa after introducing the choline chloride and glycerol, while related the crystallinity was only changed from 60.06% to 62.97%. By contrast, a more compact structure and fewer pores on the fiber surface were identified in samples with additives along with well-preserved cellulose frameworks. Besides, it should be noted that an optimization in the overall thermal stability was obtained in samples with additives. The significant effect of regenerated cellulose with the addition of glycerol was attributed to the reduction of cellulose damage by slowing down the dissolution and cross-linking in the cellulose viscose. The enhancement of the physical strength of regenerated cellulose fiber can be realized by the appropriate adjustment of the hydrogen bond distribution in the ionic liquid system with additives.

A deep eutectic solvent (DES) composed of sulfamic acid and glycerol allowed for the sustainable preparation of cellulose nanofibrils (CNF) with simultaneous sulfation. The reaction time and the levels of sulfamic acid demonstrated that fibers could be swelled and sulfated simultaneously by a sulfamic acid-glycerol-based DES and swelling also promoted sulfation with a high degree of substitution (0.12). The DES-pretreated fibers were further nanofibrillated by a grinder producing CNF with diameters from 10 nm to 25 nm. The crystallinity ranged from 53–62%, and CNF maintained the original crystal structure. DES pretreatment facilitated cellulose nano-fibrillation and reduced the energy consumption with a maximum reduction of 35%. The films prepared from polyvinyl alcohol (PVA) and CNF showed good UV resistance ability and mechanical properties. This facile and efficient method provided a more sustainable strategy for the swelling, functionalization and nano-fibrillation of cellulose, expanding its application to UV-blocking materials and related fields.

In this study, a novel type of high-strength regenerated cellulose composite fiber reinforced with cellulose nanofibrils (CNFs) and nanosilica (nano-SiO₂) was prepared. Adding 1% CNF and 1% nano-SiO₂ to pulp/AMIMCl improved the tensile strength of the composite cellulose by 47.46%. The surface of the regenerated fiber exhibited a scaly structure with pores, which could be reduced by adding CNF and nano-SiO₂, resulting in the enhancement of physical strength of regenerated fibers. The cellulose/AMIMCl mixture with or without the addition of nanomaterials performed as shear thinning fluids, also known as “pseudoplastic” fluids. Increasing the temperature lowered the viscosity. The yield stress and viscosity sequences were as follows: RCF-CNF² > RCF-CNF²-SiO₂² > RCF-SiO₂² > RCF > RCF-CNF¹-SiO₂¹. Under the same oscillation frequency, G’ and G” decreased with the increase of temperature, which indicated a reduction in viscoelasticity. A preferred cellulose/AMIMCl mixture was obtained with the addition of 1% CNF and 1% nano-SiO₂, by which the viscosity and shear stress of the adhesive were significantly reduced at 80 °C.

Oxygen delignification presents high efficiency but causes damage to cellulose, therefore leading to an undesired loss in pulp strength. The effect of ionic liquid pretreatment of [BMIM][HSO₄] and [TEA][HSO₄] on oxygen delignification of the eucalyptus kraft pulp was investigated at 10% IL loading and 10% pulp consistency, after which composition analysis, pulp and fiber characterizations, and the mechanism of lignin degradation were carried out. A possible dual effect of enhancing delignification and protecting fibers from oxidation damage occurred simultaneously. The proposed [TEA][HSO₄] pretreatment facilitated lignin removal in oxygen delignification and provided fibers with improved DP, fiber length and width, and curl index, resulting in the enhanced physical strength of pulp. Particularly, its folding endurance improved by 110%. An unusual brightness reduction was identified, followed by detailed characterization on the pulps and extracted lignin with FTIR, UV, XPS, and HSQC. It was proposed that [TEA][HSO₄] catalyzed the cleavage of β-O-4 bonds in lignin during the oxygen delignification, with the formation of Hibbert’s ketones and quinonoid compounds. The decomposed lignin dissolved and migrated to the fiber surface, where they facilitated the access of the oxidation agent and protected the fiber framework from oxidation damage. Therefore, it was concluded that ionic liquid pretreatment has a dual effect on oxygen delignification.