Cellulose-based Materials Research Articles

"Bottom-up" and "top-down" strategies toward strong cellulose-based materials.

Cellulose, as the most abundant natural polymer on Earth, has long captured researchers' attention due to its high strength and modulus. Nevertheless, transferring its exceptional mechanical properties to macroscopic 2D and 3D materials poses numerous challenges. This review provides an overview of the research progress in the development of strong cellulose-based materials using both the "bottom-up" and "top-down" approaches. In the "bottom-up" strategy, various forms of regenerated cellulose-based materials and nanocellulose-based high-strength materials assembled by different methods are discussed. Under the "top-down" approach, the focus is on the development of reinforced cellulose-based materials derived from wood, bamboo, rattan and straw. Furthermore, a brief overview of the potential applications fordifferent types of strong cellulose-based materials is given, followed by a concise discussion on future directions.

Preparation of a bifunctional precursor with antibacterial and flame retardant properties and its application to cotton fabrics

Cotton fabric is a cellulose-based material with complex capillary spaces, which enhance breathability and softness. However, these capillary spaces can promote bacterial growth with moisture during storage and daily use. Additionally, cotton fibers are highly flammable, posing a fire hazard to wearer. The lack of inherent antibacterial and flame retardant properties in cotton fabric limits its applications. In this paper, the triazole compound containing Schiff base (NABTA) was synthesized from 3-bromopropene, p-hydroxybenzaldehyde and 3-amino-1,2,4-triazole, followed by an addition reaction between Schiff base activity and 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO) to synthesize an antibacterial and flame retardant precursor (NABTA-DOPO). The structure of NABTA and NABTA-DOPO was characterized by FTIR and NMR. NABTA and NABTA-DOPO were applied to cotton fabrics to investigate and compare their antibacterial properties and thermal stability. The results showed that all the cotton fabrics treated with NABTA and NABTA-DOPO had favorable antibacterial effects. The introduction of DOPO had no significant effect on the antibacterial effect and mechanism of the fabrics. However, it otherwise improved the burning stability of treated cotton fabrics. The antibacterial activity of 10 g/L NABTA-DOPO treated cotton fabrics after chlorination against E. coli and S. aureus was over 99.99 %. The vertical burning test results showed that cotton fabrics treated with a concentration of 50 g/L NABTA-DOPO had improved flame retardant properties with a damaged length of 5.9 cm. In addition, the storage, washability, UV stability and antibacterial reproducibility experiments demonstrated the excellent durability and reproducibility of the N-halamine structure of chlorinated cotton fabrics. This study enhances cotton fabric by synthesizing and applying NABTA and NABTA-DOPO, resulting in improved multifunctionalities, including antibacterial properties, flame retardancy, UV resistance, and wettability.

Coordination-driven in-situ controlled synthesis of cellulose-based fluorescent composite with tunable color for decoration, anti-counterfeiting, and accurate color recognition

Fluorescent composites have widespread applications in many aspects. Wood-derived cellulose is a renewable, easily processed and biodegradable, and cellulose-based fluorescent composites are highly favored for in different fields. However, the existing cellulose-based fluorescent composites still have many urgent problems to be solved, such as unstable luminescence properties and easy shedding of luminescent substances, and the development of their practical applications is still a formidable challenge. Herein, a green and mild strategy for the in-situ controllable synthesis of cellulose-based fluorescent composites membrane (CFM) was developed. Firstly, delignified wood (DW) was modified with citric acid, and then lanthanide ions were introduced on modified DW through coordinated covalent bonds. Additionally, the luminescence mechanism of CFM is proposed. CFMs show adjustable color for decorative and light conversion and can be accurately identified for data protection, which increases the high value-added of cellulose-based composites. The stable luminescent properties were maintained after sonication for 30 min or solvent immersion for three months. Therefore, this work presents a new approach for the synthesis of CFM, which provides an environment-friendly strategy for manufacturing cellulose-based fluorescent materials, which is significant for the subsequent development of environment-friendly composites for anti-counterfeiting and decorative applications.

Antifungal activity of carvacrol-based solids and their effects on Whatman and Kraft paper

The degradation of cellulose-based materials by fungi represents a menace to the cultural heritage conservation. Carvacrol-based β-cyclodextrins and cocrystals proved effective antifungal remedies in vitro but their effects on paper structure and properties were not studied. The aim of this study was to investigate possible structural modifications and alterations of the mechanical, optical and chemical properties of artificially aged and unaged Whatman and Kraft paper subjected to the treatment with carvacrol-based β-ciclodextrins and cocrystals. The pH of the samples did not significantly change after the treatment, as well as no colour-related alterations were detected (1.00<ΔE<2.00). The tensile strength of both Whatman and Kraft paper was not affected by the vapours of carvacrol and spectroscopic analysis (FTIR and XRD) revealed no carvacrol-related damages of paper structure. The antifungal efficacy of the carvacrol-cocrystal was also proved on a book prototype made of Whatman and Kraft paper, kept under 98% of humidity for 28 days, and purposely inoculated with a mix of fungal species (A. alternata, Aspergillus sp. section Nigri, C. cladosporioides, and T. orientale). These results show the applicability of a carvacrol-releasing system, effective as antifungal remedy, and at the same time not harmful to Whatman and Kraft paper, as these materials did not show treatment-induced degradation.

The impact of the carbohydrate-binding module on how a lytic polysaccharide monooxygenase modifies cellulose fibers

BackgroundIn recent years, lytic polysaccharide monooxygenases (LPMOs) that oxidatively cleave cellulose have gained increasing attention in cellulose fiber modification. LPMOs are relatively small copper-dependent redox enzymes that occur as single domain proteins but may also contain an appended carbohydrate-binding module (CBM). Previous studies have indicated that the CBM “immobilizes” the LPMO on the substrate and thus leads to more localized oxidation of the fiber surface. Still, our understanding of how LPMOs and their CBMs modify cellulose fibers remains limited.ResultsHere, we studied the impact of the CBM on the fiber-modifying properties of NcAA9C, a two-domain family AA9 LPMO from Neurospora crassa, using both biochemical methods as well as newly developed multistep fiber dissolution methods that allow mapping LPMO action across the fiber, from the fiber surface to the fiber core. The presence of the CBM in NcAA9C improved binding towards amorphous (PASC), natural (Cell I), and alkali-treated (Cell II) cellulose, and the CBM was essential for significant binding of the non-reduced LPMO to Cell I and Cell II. Substrate binding of the catalytic domain was promoted by reduction, allowing the truncated CBM-free NcAA9C to degrade Cell I and Cell II, albeit less efficiently and with more autocatalytic enzyme degradation compared to the full-length enzyme. The sequential dissolution analyses showed that cuts by the CBM-free enzyme are more evenly spread through the fiber compared to the CBM-containing full-length enzyme and showed that the truncated enzyme can penetrate deeper into the fiber, thus giving relatively more oxidation and cleavage in the fiber core.ConclusionsThese results demonstrate the capability of LPMOs to modify cellulose fibers from surface to core and reveal how variation in enzyme modularity can be used to generate varying cellulose-based materials. While the implications of these findings for LPMO-based cellulose fiber engineering remain to be explored, it is clear that the presence of a CBM is an important determinant of the three-dimensional distribution of oxidation sites in the fiber.

Model systems for clarifying the effects of surface modification on fibre–fibre joint strength and paper mechanical properties

The growing demand for sustainable products has spurred research into renewable materials, with cellulose-based materials emerging as prominent candidates due to their exceptional properties, abundance, and wide-ranging applications. In this context, there is a need to develop a better fundamental understanding of cellulose interactions such that we can continue to design and improve sustainable materials. Individual interactions can be difficult to assess in bulk fibre-based materials and therefore cellulose model materials have become indispensable tools for researchers as they can facilitate the study of cellulose interactions at a molecular level enabling the design of sustainable materials with enhanced properties.This study presents a new methodology for studying the effects of surface treatments on the individual fibre–fibre joint strength using wet-spun cellulose nanofiber (CNF) filaments as model materials. The Layer-by-Layer assembly technique is used to modify the surface chemistry of the model materials as well as bleached and unbleached hardwood Kraft fibres, demonstrating its potential to enhance adhesive properties and overall mechanical performance of papers made from these fibres. The study further explores the impact of increasing network density through wet-pressing during paper preparation, showcasing a comprehensive approach to molecularly tailor fibre-based materials to achieve superior mechanical properties. The proposed methodology provides a time-efficient evaluation of chemical additives in paper preparation.

Fabrication of liquid-free ionic conductive elastomer (ICE) from cellulose-rosin derived poly(esterimide) towards temperature-tolerant and solvent-resistant UV shadowless adhesive and sensor

Recently, the utilization of the cellulose to fabricate the multifunctional materials with aim to replace the petroleum-based product, is receiving significant attentions. However, the development of cellulose-based multifunctional materials with high mechanical strength and temperature resistance is still a challenge. Herein, the intrinsic feature and property of cellulose and rosin were creatively employed to fabricate a novel cellulose-rosin based poly(esterimide) (PEI) by esterification reaction and imidization reaction, and the obtained cellulose-rosin derived PEI exhibits superior thermal stability. Then the as-prepared cellulose-rosin derived PEI was dissolved in polymerizable deep eutectic solvents (PDES) and in-situ formed the ionic conductive elastomer (ICE) with via UV-induced polymerization. These cellulose-rosin based ICE exhibited excellent mechanical properties, solvent resistance, and temperature tolerance. By adjusting the mass ratio of cellulose-rosin derived PEI and PDES, the as-prepared liquid-free ICE functions as UV shadowless adhesive and wearable sensors. The bonding strength of UV shadowless adhesive could 1.52 MPa, which could be applied to fix the broken glass toy models. Furthermore, wearable sensors based those ICE could monitor the large and subtle movements even under extreme environmental condition, such as being soaked in organic solvent (such as tetrahydrofuran) or at low/high temperature (−25 °C or 80 °C). This work opens a new avenue for the next-generation of multifunctional ICE.

A Novel Cellulose-Based Composite Hydrogel Microsphere Material: for Efficient Adsorption of Co(II) and Ni(II) Ions in Water

A Novel Cellulose-Based Composite Hydrogel Microsphere Material: for Efficient Adsorption of Co(II) and Ni(II) Ions in Water

A cellulose-based light-management film incorporated with benzoxazine resin/tannic acid exhibiting UV/blue light double blocking and enhanced mechanical property

Cellulose, as a biomass resource, has attracted increasingly attention and extensive research by virtue of its widely sources, ideal degradability, good mechanical properties and easy modification due to its rich hydroxyl groups. Nevertheless, it is still a challenge to attain high performance cellulose-based composite film materials with diverse functional combinations. In this work, we developed a multifunctional cellulose-based film via a facile impregnation-curing strategy. Here, benzoxazine resin (BR) is used as an optically functional component to endow the microfibrillated cellulose (MFC) film with powerful light management capabilities including UV and blue light double shielding, high transmittance, and high haze. Meanwhile, the introduction of tannic acid (TA) substantially enhanced the mechanical properties of the film, including tensile strength and toughness, by constructing energy-sacrificial bonds. An effective self-healing of the film was achieved by controlling the degree of BR curing. The final films exhibited 98.24 % UV shielding and 89.98 % blue light blocking, good mechanical properties including a tensile strength of 202.21 MPa and tensile strain of 7.1 %, as well as desirable thermal healing properties supported by incompletely cured BR. This work may provide new insights into the high-value utilization of biomass resources.

Study of the effect of bleaching agents on the crystalline index of cellulose-based materials derived from corn husk by CP/MAS 13C NMR and FT-IR spectroscopies

This work proposes an evaluation of the Crystalline Index (CrI) in function of the bleaching process employed during cellulose extraction from corn husk, for further characterization using CP/MAS 13C NMR, XRD, and FT-IR. In that sense, CrI values were calculated by FT-IR and the bands associated with the crystalline and amorphous regions were observed at 1424 cm−1 and 896 cm−1, respectively. Similarly, the signals due to ordered (89.1 ppm) and disordered (84.2 ppm) cellulose chains were detected by solid-state 13C NMR, while the Segal equation was only used for comparison purposes. Additionally, PCA studies showed consistent results attributed to the crystalline region in cellulose domains analyzed by both, FT-IR and solid-state 13C NMR. The results revealed the coexistence of cellulose I/cellulose II and its effect on CrI, as well as the incomplete mercerization process, in some cases non-cellulosic residues can cause an overestimation of CrI. Additionally, the thermal stability and the glass transition temperature were determined by TGA/DTA and DSC analyses. Finally, a partially fibrillated-network morphology with a diameter of 20.47 ± 2.77 μm was observed in cellulose bleached with peracetic acid, whereas organosolv method provides flexible and clean microfibrils with diameter sizes between 10 and 9 μm.

Nanocellulose-Based Materials for Water Pollutant Removal: A Review.

Cellulose in the nano regime, defined as nanocellulose, has been intensively used for water treatment. Nanocellulose can be produced in various forms, including colloidal, water redispersible powders, films, membranes, papers, hydrogels/aerogels, and three-dimensional (3D) objects. They were reported for the removal of water contaminants, e.g., heavy metals, dyes, drugs, pesticides, pharmaceuticals, microbial cells, and other pollutants from water systems. This review summarized the recent technologies for water treatment using nanocellulose-based materials. A scientometric analysis of the topic was also included. Cellulose-based materials enable the removal of water contaminants, and salts offer advanced technologies for water desalination. They are widely used as substrates, adsorbents, and catalysts. They were applied for pollutant removal via several methods such as adsorption, filtration, disinfection, coagulation/flocculation, chemical precipitation, sedimentation, filtration (e.g., ultrafiltration (UF), nanofiltration (NF)), electrofiltration (electrodialysis), ion-exchange, chelation, catalysis, and photocatalysis. Processing cellulose into commercial products enables the wide use of nanocellulose-based materials as adsorbents and catalysts.

Exploring a cellulose-immobilized bacteria for self-healing concrete via microbe-induced calcium carbonate precipitation

Concrete is widely used in modern civil engineering due to its high compressive strength, abundance of raw materials, and simple production process. However, its brittleness makes it vulnerable to environmental factors, leading to cracks that impact its durability. Microbial-induced carbonate precipitation (MICP) technology has emerged as a promising solution, offering environmental benefits, real-time repair capabilities, and reduced manual intervention. This study focuses on enhancing the efficiency of calcium sources by identifying a strain with calcium ion adsorption abilities and pairing it with a mineralizing bacterium rich in urease production. Microorganisms were immobilized in a microcapsule using a cellulose-based material to explore the potential of cellulosic gel as a bacterial carrier. The gel was prepared through a sol-gel transformation process, incorporating a porogen to create a porous structure. Microcapsules with a particle size of 2.5–3.0 mm were successfully produced, enhancing their mechanical strength by 88.29 %. Examination of the microscopic structure of the cellulosic gel demonstrated its strong immobilization capacity for bacterial spores. The self-repairing effect of the gel on cracks was particularly effective under water curing conditions at 30–40 °C. After 28 days, cracks up to 0.3 mm wide were repaired, with a repair rate exceeding 90 % for cracks 0.1–0.2 mm wide.

Bio-Based Materials as a Sustainable Solution for the Remediation of Contaminated Marine Sediments: An LCA Case Study.

Contaminated sediments may induce long-term risks to humans and ecosystems due to the accumulation of priority and emerging inorganic and organic pollutants having toxic and bio-accumulation properties that could become a secondary pollution source. This study focused on the screening of novel bio-based materials to be used in the decontamination of marine sediments considering technical and environmental criteria. It aimed to compare the environmental impacts of cellulose-based adsorbents produced at lab scale by using different syntheses protocols that involved cellulose functionalization by oxidation and branching, followed by structuring of an aerogel-like material via Soxhlet extraction and freeze-drying or their combination. As model pollutants, we used 4-nitrobenzaldehyde, 4-nitrophenol, methylene blue, and two heavy metals, i.e., cadmium and chromium. When comparing the three materials obtained by only employing the Soxhlet extractor with different solvents (without freeze-dying), it was observed that the material obtained with methanol did not have a good structure and was rigid and more compact than the others. A Life Cycle Assessment (LCA) was conducted to evaluate the environmental performance of the novel materials. Apart from the hierarchical categorization of the materials based on their technical and environmental performance in eliminating organic pollutants and heavy metal ions, it was demonstrated that the cellulose-based material obtained via Soxhlet extraction with ethanol was a better choice, since it had lower environmental impacts and highest adsorption capacity for the model pollutants. LCA is a useful tool to optimize the sustainability of sorbent materials alongside lab-scale experiments and confirms that the right direction to produce new performant and sustainable adsorbent materials involves not only choosing wastes as starting materials, but also optimizing the consumption of electricity used for the production processes. The main results also highlight the need for precise data in LCA studies based on lab-scale processes and the potential for small-scale optimization to reduce the environmental impacts.

STUDY OF SILVER ADSORPTION ON CELLULOSE-BASED BIOSORBENTS

The survey aimed to investigate the adsorption properties of cellulose-based materials derived from cereal by-products towards Ag+ ions in water solutions, and to shed light on the mechanism of adsorption. Cellulose was isolated from rice and einkorn husks using alkali and bleaching treatments. Untreated einkorn husks and commercial cellulose served as reference samples. Characterization techniques included XRD, FTIR, SEM, and low-temperature nitrogen adsorption, with surface elemental composition analyzed by XPS. The study examined how contact time, initial silver ion concentration, pH, and temperature affected adsorption. The adsorption process was modeled using pseudo-second-order and Langmuir models, and thermodynamic parameters were evaluated. All materials showed potential as effective Ag+ ion adsorbents, indicating their suitability for creating silver-modified catalytic materials.

Green reduction of ZnO nanoparticles using cationic dialdehyde cellulose (cDAC) for efficient Congo red dye removal

More sustainable materials have been becoming an important concern of worldwide scientists, and cellulosic materials are one alternative in water decontamination. An efficient strategy to improve removal capacity is functionalizing or incorporating nanomaterials in cellulose-based materials. The new hybrid cDAC/ZnONPs was produced by green synthesis of zinc oxide nanoparticles (ZnONPs), promoting the in situ reduction and immobilization on the cationic dialdehyde cellulose microfibers (cDAC) surface to remove Congo red dye from water. cDAC/ZnONPs was characterized by scanning electron microscopy (SEM-EDS) and infrared spectroscopy (FTIR), which showed efficient nanoparticles reduction. Adsorption efficiency on cationic cellulose surface was investigated by pH, contact time, initial concentration, and dye selectivity tests. The material followed the H isotherm model, which resulted in a maximum adsorption capacity of 1091.16 mg/g. Herein, was developed an efficient and ecologically correct new adsorbent, highly effective in Congo red dye adsorption even at high concentrations, suitable for the remediation of contaminated industrial effluents.

Efficient cellulose dissolution and derivatization enabled by oxalic/sulfuric acid for high-performance cellulose films as food packaging

The performance of cellulose-based materials is highly dependent on the choice of solvent systems. Exceptionally, cellulose dissolution and derivatization by efficient solvent have been considered as a key factor for large-scale industrial applications of cellulose. However, cellulose dissolution and derivatization often requires harsh reaction conditions, high energy consumption, and complex solubilizing, resulting in environmental impacts and low practical value. Here we address these limitations by using a low-temperature oxalic acid/sulfuric acid solvent to enable cellulose dissolution and derivatization for high-performance cellulose films. The dissolution and derivatization mechanism of the mixed acid is studied, demonstrating that cellulose is firstly socked by oxalic acid, then more hydrogen bonds ionized by sulfuric acid break cellulose chain, and finally the esterification reaction between oxalic acid and cellulose is catalyzed by sulfuric acid. Solutions containing 8 %–10 % cellulose are obtained and can be stored for a long time at −18 °C without significant degradation. Moreover, the cellulose film exhibits a higher tensile strength of up to 66.1 MPa, thermal stability, and degree of polymerization compared to that fabricated by sulfuric acid. These unique advantages provide new paths to utilize renewable resources for alternative food packaging materials at an industrial scale.

An Evaluation of the Fire Safety of Waste Paper-Based Internal Finishing Materials Combined with Expandable Graphite According to Changes in Magnesium Hydroxide Content

Inflammable building finishing materials act as a major cause of fire propagation, and they, therefore, pose significant risks to life and can lead to property damage. To replace such flammable building finishing materials, many countries have established regulations limiting their use, which has led to extensive research on the development of flame-retardant building finishing materials. Such methods have included adding flame retardants to construction materials to reduce the heat release rate and total heat release. The present study aimed to enhance the fire performance of cellulose-based architectural finishing materials by creating a dual flame-retardant mixture using expandable graphite and magnesium hydroxide added to recycled paper waste. Specimen fabrication involves using a pressing method to apply uniform pressure to compress the mixture in a mold. The total heat release (THR), CO, and CO2 production of the produced specimens were measured using a cone calorimeter while varying the magnesium hydroxide additive ratio. The combustion gases were measured through NES 713 experiments to determine any changes in the Toxic Index corresponding to variations in the magnesium hydroxide content. The experiment results established a correlation between the magnesium hydroxide additive ratio and the total heat release, as well as the existence of variations in CO and CO2 production for the dual flame-retardant recycled paper material. A database for combustion gases was also obtained. It was confirmed that the fire performance was improved by confirming that the total heat release decreased by 52% from the previous one in the magnesium hydroxide content of 30 g, and it was confirmed that the inflection points of the Toxic Index value due to the change in CO and CO2 gas production occurred in the magnesium hydroxide content of 20 g due to the improvement of the fire performance. Through the ISO 5660-1 experiment data, we have secured data that can be used as foundational information for performance-oriented fire risk assessments, thereby ensuring the fire safety of cellulose materials that are vulnerable to fire.

A Study on the Evaluation of Thermal Insulation Performance of Cellulose-Based Silica Aerogel Composite Building Materials.

Buildings utilize both inorganic and organic insulation materials to conserve energy and prevent heat loss. However, while exhibiting excellent thermal insulation performance, organic insulation materials increase the risk of fire due to the emission of intense heat and toxic smoke in the event of a fire. Conversely, inorganic insulation materials are characterized by a lower thermal insulation performance, leading to an increase in the weight of the building with extensive use. Therefore, the necessity for research into new insulation materials that address the drawbacks of existing ones, including reducing weight, enhancing fire resistance, and improving thermal insulation performance, has been recognized. This study focuses on evaluating the enhancement of the thermal insulation performance using novel building materials compared to conventional ones. The research methodology involved the incorporation of porous aerogel powders into paper-based cellulose insulation to improve its insulating properties. Samples were prepared in standard 100 × 100 mm2 panel forms. Two control groups were utilized: a pure control group, where specimens were fabricated using 100% recycled cardboard for packaging, and a mixed control group, where specimens were produced using a mixture ratio of 30 wt% ceramic binder and 40 wt% expandable graphite. Experimental group specimens were prepared by increasing the aerogel content from 200 to 1000 mL under each condition of the control groups (pure and mixed) after mixing. The thermal insulation performance of the specimens was evaluated in terms of thermal conductivity and thermal diffusivity according to ISO 22007-2 (for solids, paste, and powders). Through this study, it was found that the thermal insulation performances of the pure control and experimental groups improved by 16.66%, while the mixed control and experimental groups demonstrated a 17.06% enhancement in thermal insulation performance with the addition of aerogel.

Recent Advances in Functional Cellulose-Based Materials: Classification, Properties, and Applications

Recent Advances in Functional Cellulose-Based Materials: Classification, Properties, and Applications

Cellulose-Based Materials for The Consolidation of Archaeological Wooden Artifacts: Review Article

Cellulose-Based Materials for The Consolidation of Archaeological Wooden Artifacts: Review Article