Rational Design of Cellulose Nanofibrils Separator for Sodium-Ion Batteries.

Cellulose nanofibrils (CNF) with high thermal stability and excellent electrolyte wettability attracted tremendous attention as a promising separator for the emerging sodium-ion batteries. The pore structure of the separator plays a vital role in electrochemical performance. CNF separators are assembled using the bottom-up approach in this study, and the pore structure is carefully controlled through film-forming techniques. The acid-treated separators prepared from the solvent exchange and freeze-drying demonstrated an optimal pore structure with a high electrolyte uptake rate (978.8%) and Na+ transference number (0.88). Consequently, the obtained separator showed a reversible specific capacity of 320 mAh/g and enhanced cycling performance at high rates compared to the commercial glass fiber separator (290 mAh/g). The results highlight that CNF separators with an optimized pore structure are advisable for sodium-ion batteries.

Robust holocellulose barrier films from agricultural byproduct of Camellia Oleifera shells through dilute acid and ultrasonic treatments.

Camellia oleifera shells (COS) are commonly discarded as an agricultural by-product. Effective utilization of COS can not only reduce environmental pollution but also enhance the value of the tea-oil industry. The unique composition of COS, with high hemicellulose and low cellulose content, makes it suitable for the production of film materials. In this study, COS holocellulose (COSH) was isolated and treated with four different types of dilute acids (15 % acetic acid, gallic acid, citric acid, and 0.5 % sulfuric acid, 1-24 h, 75°-105 °C) to produce barrier films. Among these, citric acid treatment resulted in the strongest and toughest film. By incorporating a brief ultrasonic pretreatment (15 min, 300 w) prior to the citric acid reaction, translucent films were achieved with impressive mechanical properties, showing tensile strength, Young's modulus and elongation at break up to 75.72 MPa, 3306.11 MPa and 8.01 %, respectively. Through a comprehensive analysis of the structure-property relationships, it was discovered that the combined effects of ultrasonic and citric acid treatments disrupted the integrated holocelluose fiber structure and facilitated the formation of a robust hydrogen bond network during the film preparation process. The resulting films exhibited enhanced water vapor barrier properties, antioxidant capacity, and complete decomposition in soil, suggesting the potential application as wraps for fresh fruits.

Mechanical, thermal, and water absorption properties of HDPE/barley straw composites incorporating waste rubber.

This study investigates the mechanical, thermal, and water absorption properties of high-density polyethylene (HDPE) composites filled with barley straw and varying amounts of waste rubber. The research aims to develop sustainable materials that repurpose agricultural and industrial waste while addressing resource scarcity and waste management challenges. Composites were prepared using a twin-rotor mixer and hydraulic press, with waste rubber content varying from 0 to 20 wt%. Mechanical properties were evaluated through tensile testing, thermal behavior was analyzed using TGA, DTG, and DSC, and long-term water absorption was measured. Results show that increasing waste rubber content from 0 to 20% led to a decrease in tensile strength (11.3 to 8.9 MPa) and tensile modulus (1760 to 790 MPa), while relative extension increased (2.4-5.9%). Thermal analysis revealed a slight reduction in onset degradation temperature (270 °C to 240 °C) and increased char residue (8-18%) with higher rubber content. Water absorption decreased significantly, from 12 to 13% to 6-7% after 600 h of immersion, as waste rubber content increased. These findings demonstrate that incorporating waste rubber into HDPE/barley straw composites results in materials with enhanced flexibility and water resistance at the cost of some strength and stiffness. In conclusion, the results of this study offer a clear pathway for the development of sustainable polymer composites that have broad potential applications across industries like construction, marine infrastructure, automotive, and packaging. By replacing traditional, resource-intensive materials with eco-friendly alternatives, these composites not only provide functional benefits but also support global efforts toward sustainable development and environmental conservation.

Cell Wall Modification Based on Combination Reagents to Improve Dimensional Stability of Wood with High Efficiency.

Although γ-methacryloxypropyltrimethoxysilane (MPS) was proved to be an effective reagent for improving the dimensional stability of wood, a bottleneck in ASE value (around 50%) existed. The reason was that MPS with low polarity opened few hydrogen bonds in the amorphous region of cellulose, while these hydrogen bonds could be reopened by water. Therefore, citric acid (CA) is chosen to cooperate with MPS to further enhance the dimensional stability of wood. In this paper, MPS and CA were used to modify wood individually (MW and CW) or with different combinations, that is, one-step modification (M/CW) and two-step modification with MPS first (M-CW) or CA first (C-MW). CA and MPS concentrations were optimized at 5 wt%. The ASE value for M/CW was only 25.74% at a weight percent gain (WPG) of 6.43%, which was only 0.6 times to MW or 0.7 times to CW. For M-CW, the ASE value gradually decreased with the soaking cycles, from 65.64% at a WPG of 9.05% to 51.20%. The C-MW had the best dimensional stability, with the ASE value 75.35% at a WPG of 11.50%. Although it decreased during the first soaking cycle, it stabilized at 62.20% at last. SEM and EDS images showed that the polymer mainly distributed in cell walls and few in cell lumen in C-MW. Thus, the enhanced dimensional stability of C-MW could be explained by CA opening the hydrogen bonds in the amorphous region of cellulose first, which provided more binding sites for MPS.

Quantitative analysis of intermolecular forces in cellulose microfibrils and hemicellulose with AFM nano-colloidal probes.

It is an interesting research topic to study the interfacial interactions between hemicellulose and cellulose, specifically how hemicellulose's structure affects its binding to cellulose nanofibers. Our research proposes that dispersion interaction play an important role in this interfacial interaction, more so than electrostatic forces when considering the adherence of cellulose to xylan. To quantify these interactions, the Atomic Force Microscope (AFM) colloidal probe technique is applied to measure the intermolecular forces between cellulose nanofibers, which are attached to the probe and xylan. These measured forces are then analyzed in relation to the length, diameter and functional groups of the nanocellulose, as well as the molecular weight and side chains of the xylan. Moreover, the predominance of dispersion forces by contrasting the adhesive forces before and after the grafting of a large nonpolar group onto xylan. This modification significantly reduces contact between the cellulose and xylan backbone, thereby markedly diminishing the dispersion interactions. Parallel to the AFM experiments, molecular dynamics (MD) simulations corroborate the experimental results and support our hypotheses. Collectively, these findings contribute to a deeper understanding of polysaccharide interactions within lignocellulose.

Facile preparation of cellulose nanocrystals/ZnO hybrids using acidified ZnCl2 as cellulose hydrolytic media and ZnO precursor.

Hybridization of nanocellulose with zinc oxide nanoparticles can improve the dispersibility of the zinc oxide and bring new functions to the bio-based products. In this study, cellulose nanocrystal/zinc oxide (CNC/ZnO) nanohybrids with reinforcing and antibacterial properties were prepared via a facile one-pot route. Microcrystalline cellulose (MCC) was first treated with acidified zinc chloride and hydrolyzed into CNCs, which then served as a stabilizing and supporting agent for the in-situ growth of ZnO nanoparticles during subsequent chemical precipitation. The acidified ZnCl2 solution played a dual role, acting both as cellulose hydrolytic media and as ZnO precursor. By adjusting the pH of the zinc precursor solution (pH = 9-12), well-dispersed rod-like (length: 137.0-468.0 nm, width: 54.1-154.1 nm) and flower-like (average diameter: 179.6 nm) ZnO nanoparticles with hexagonal wurtzite structure were obtained. CNC/ZnO nanohybrids were incorporated into waterborne polyurethane (WPU) films. The Young's modulus and tensile strength of the nanocomposite films increased gradually from 154.8 to 509.0 MPa and from 16.5 to 29.9 MPa, respectively, with increasing CNC/ZnO nanofiller content up to 10 wt%. The 10 % CNC/ZnO composites showed inhibition rates to both E. coli and S. aureus above 88.8 %.

Heat Transfer Efficiency and pMDI Curing Behavior during Hot-Pressing Process of Tea Oil Camellia (Camellia Oleifera Abel.) Shell Particleboard.

The use of agricultural biomass composites as new construction and building materials has grown rapidly in recent decades. Considering that energy consumption is one of the most important factors in production, the aim of this work is to examine how heat transfer is affected at various ratios and combinations of three-layer tea oil camellia shell (TOCS) based particleboard with the purpose of creating a mat-forming structure, which has the best physical and mechanical properties for furniture and construction use in a dry environment and consumes the least amount of energy. Additionally, it investigated how raw materials type affects the curing process of polymeric methylene diisocyanate (pMDI) using differential scanning calorimetry (DSC). According to the obtained data, the centerline temperature could reach a maximum of 125 °C after 3 min regardless of the materials or combinations, while the pMDI curing time was 100-110 °C. The results demonstrated that efficient heat transfer could help resin polymerization and improve panel properties. The effect of raw materials on the curing behavior of resin indicated that TOCS particles somehow caused more heat reactions at the curing point. It appeared that particleboard with a ratio of 40% commercial wood particles in the surface layers and 50% TOCS particles (mesh size: -3 + 14) in the core layer with a modulus of rupture (MOR) of 11.29 N/mm2 and internal bonding (IB) of 0.78 N/mm2 has the best properties and met EN 312: 2010 standard requirements for particleboard P2.

Mechanically strong and biodegradable holocellulose films prepared from Camellia oleifera shells.

Bioplastic derived from renewable lignocellulosic biomass is an attractive alternative to petroleum-based plastics. Herein, Callmellia oleifera shells (COS), a unique byproduct from tea oil industry, were delignified and converted into high-performance bio-based films via a green citric acid treatment (15 %, 100 °C and 24 h), taking advantage of their high hemicellulose content. The structure-property relations of COS holocellulose (COSH) films were systematically analyzed considering different treatment conditions. The surface reactivity of COSH was improved via a partial hydrolysis route and strong hydrogen bonding formed between the holocellulose micro/nanofibrils. COSH films exhibited high mechanical strength, high optical transmittance, improved thermal stability, and biodegradability. A mechanical blending pretreatment of COSH, which disintegrated the COSH fibers before the citric acid reaction, further enhanced the tensile strength and Young's modulus of the films up to 123.48 and 5265.41 MPa, respectively. The films decomposed completely in soil, demonstrating an excellent balance between degradability and durability.

Facile synthesis of nanocellulose-based Cu2O/Ag heterostructure as a surface-enhanced Raman scattering substrate for trace dye detection.

Semiconductor metal-oxide/metal heterostructures with synergetic properties have potential applications in photocatalysis and optical sensors. Here, Cu2O sub-micro cubes were synthesized under environmentally benign conditions using 2, 2, 6, 6-tetramethylpyperdine-1-oxyl (TEMPO)-oxidized cellulose nanofibrils as a reducing and stabilizing agent. Then the surface of the Cu2O cubes was decorated with silver nanoparticles (AgNPs) by a substitution reaction. The Cu2O/Ag heterostructures within the cellulose nanofibrils (CNFs) network were employed as a promising surface-enhanced Raman scattering (SERS) assay for efficient sensing of methylene blue (MB), reaching a maximum enhancement factor (EF) of 4.0 × 104. Their SERS intensities depended on the coverage density of AgNPs and the wavelength of the excitation laser. The excellent SERS performance may result from the charge transfer between Ag and Cu2O molecules and the strong electromagnetic field at the interface. The CNF-Cu2O/Ag substrates were capable of detecting MB dye down to 10-8 M level with a relative standard deviation of 10-15%, demonstrating great sensitivity and reproducibility.

Resistance to Growth of Molds for Wood Modified with Hydrophobic Hybrid Silica Gel Containing Copper Amine Complexes.

Complexation copper with amine provides an effective strategy for fixation copper in wood, while hydrophobic modification improves the dimensional stability of wood. Thus, a combination of complexation and hydrophobization is expected to enhance the efficiency of copper-based biocides. In this study, hydrophobic hybrid silica gel containing copper amine complexes (MACu) was prepared through an in situ sol-gel process in wood using methyltriethoxysilane (MTES), 3-amino-propyltriethoxysilane (APTES), and copper chloride. The resistance to growth of molds for MACu modified wood (Populus tomentosa) was measured according to ASTM D3273-16. A leaching resistance test was carried out in accordance with AWPA E11-16. The results showed that only Aspergillus niger covered the surface of untreated wood blocks and no mold grew on the MACu surface even after the leaching test. MACu xerogel and MACu wood were further characterized by SEM-EDS, FTIR, and XPS. A possible schematic diagram of the reaction mechanism was proposed to explain the high-efficiency anti-mold performance of MACu wood.

Enhanced Water Resistance of Recycled Newspaper/High Density Polyethylene Composite Laminates via Hydrophobic Modification of Newspaper Laminas.

A high strength recycled newspaper (NP)/high density polyethylene (HDPE) laminated composite was developed using NP laminas as reinforcement and HDPE film as matrix. Herein, NP fiber was modified with stearic acid (SA) to enhance the water resistance of the NP laminas and NP/HDPE composite. The effects of heat treatment and SA concentration on the water resistance and tensile property of NP and composite samples were investigated. The chemical structure of the NP was characterized with X-ray diffractometer, X-ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared spectra techniques. The surface and microstructure of the NP sheets were observed by scanning electron microscopy. An expected high-water resistance of NP sheets was achieved due to a chemical bonding that low surface energy SA were grafted onto the modified NP fibers. Results showed that the hydrophobicity of NP increased with increasing the stearic acid concentration. The water resistance of the composite laminates was depended on the hydrophobicity of the NP sheets. The lowest value of 2 h water absorption rate (3.3% ± 0.3%) and thickness swelling rate (2.2% ± 0.4%) of composite were obtained when the SA concentration was 0.15 M. In addition, the introduction of SA can not only enhance the water resistance of the composite laminates, but also reduce the loss of tensile strength in wet conditions, which shows potential in outdoor applications.

Transition of cellulose supramolecular structure during concentrated acid treatment and its implication for cellulose nanocrystal yield.

Cellulose nanocrystals with cellulose I and II allomorphs (CNC-I and CNC-II) were prepared from eucalyptus cellulose I substrate by controlling the sulfuric acid hydrolysis conditions, including acid concentration (56-64 wt%), reaction temperature (45 or 60 °C) and time (10-120 min). The crystalline structures were verified by XRD and 13C-NMR. CNC-II only appeared at very restricted reaction conditions. The rapid cellulose supramolecular structure transition under sulfuric acid concentration of around 60 wt% resulted in an abrupt change in CNC yield. A maximal CNC yield of 66.7% was obtained at acid concentration of 58 wt% and reaction temperature of 60 °C. CNC-I exhibited spindle-shape, while CNC-II showed a twisted strip structure. The state of order in cellulose during the acid hydrolysis process has been studied using a coagulation method. A tentative model of CNC-I and CNC-II formation was then proposed. This work provided significant knowledge for the production of CNCs with high yield and controllable allomorph.

Biodegradable cellulose I (II) nanofibrils/poly(vinyl alcohol) composite films with high mechanical properties, improved thermal stability and excellent transparency.

Cellulose nanofibrils (CNFs) with cellulose I and II allomorphs were efficiently prepared by sulfuric acid hydrolysis of eucalyptus cellulose under three different conditions followed by mechanical treatments: (i) classical sulfuric acid hydrolysis of cellulose I (CNF-I), (ii) sulfuric acid hydrolysis of mercerized cellulose II (MNF-II), and (iii) solubilization and hydrolysis of cellulose I by concentrated sulfuric acid and subsequent recrystallization in water (RNF-II). Crystal structure, surface chemistry, morphology and thermal properties of three CNFs were investigated and compared. Three CNFs of 2-10 wt% were mixed with PVA to prepare biodegradable composite films. CNF allomorph had significant impact on crystal structure, mechanical and thermal properties of the PVA composites. The maximum Young's modulus of CNF-I/PVA, RNF-II/PVA and MNF-II/PVA were increased by 62, 32 and 44%, respectively. Addition of CNFs raised onset degradation temperature (Tonset) and thermal decomposition temperature (Tmax) of PVA nanocomposite, while decreased the melting temperature (Tm). Temperature window (Tonset - Tm) for the melt processing of nanocomposites (10 wt% CNF loading) were increased 2.8, 3.2 and 2.5 times for CNF-I/PVA, RNF-II/PVA and MNF-II/PVA, respectively. All composite films remained excellent transparency with addition of CNFs. This comparative study provided important knowledge of selecting CNF allomorph for fabrication of high-performance CNF/PVA composites.

Production and Characterization of Large-Scale Recycled Newspaper Enhanced HDPE Composite Laminates.

Recycled newspaper (NP)/high density polyethylene (HDPE) laminated composite can reach the physical and mechanical criteria for most industrial applications, which shows the potential of using solid-state waste paper in engineering materials. Herein, the effects of splicing pattern and size on the physical and mechanical properties of the laminated composite were investigated with the ultimate purpose to fabricate a large-scaleale composite. The laminated composite with a stair-like splicing had better physical and mechanical properties than that with a vertical splicing. An efficient stress transfer could be guaranteed when the distance between the two adjacent junctions were greater than a critical proportion of 1/32 of the length at longitudinal direction. The tensile and flexural properties of the large-scaleale composite with a stair-like splicing, which was fabricated at the splicing ratio of 1/32, were 109 ± 4.2 MPa (MOR), 9836 ± 411 MPa (MOE), 119 ± 7.1 MPa (MOR) and 10002 MPa ± 347 (MOE).

A Process Optimization and Performance Study of Environmentally Friendly Waste Newspaper/Polypropylene Film Layered Composites.

Waste newspaper are currently used in a single way and have low utilization rates. In this paper, the optimal process of preparing environmentally friendly layered composites by using waste newspaper combined with polypropylene film lamination was studied. The effects of hot-pressing temperature, hot-pressing time and paper content on the properties of the composites were analyzed. The results showed that under the process conditions of hot-pressing temperature 180 °C, compression time 20 min and paper content 66.7%, the obtained composite material had a flexural strength of 126 MPa, a tensile strength of 95 MPa, an impact strength of 5.3 kJ/m2 and a water absorption thickness expansion ratio of 3.2%. Tensile performance increased by 164% compared to the original waste newspaper. Compared to our previous work, the hot processing time had been cut in half and costs were lower. In terms of creep properties, the unrecoverable strain rate was reduced by 57.5% compared to pure polypropylene. The results show that the material can maintain excellent flexural strength, tensile strength and water absorption performance while making good use of waste newspaper.

Cellulose Nanofibril/Carbon Nanomaterial Hybrid Aerogels for Adsorption Removal of Cationic and Anionic Organic Dyes.

Advances in nanoscale science and engineering are providing new opportunities to develop promising adsorbents for environmental remediation. Here, hybrid aerogels are assembled from cellulose nanofibrils (CNFs) and carbon nanomaterials to remove cationic dye methylene blue (MB) and anionic dye Congo red (CR) in single and binary systems. Two classes of carbon nanomaterials, carbon nanotubes (CNTs) and graphene nanoplates (GnPs), are incorporated into CNFs with various amounts, respectively. The adsorption, mechanics and structure properties of the hybrid aerogels are investigated and compared among different combinations. The results demonstrate CNF-GnP 3:1 hybrid exhibits the best performance among all composites. Regarding a single dye system, both dye adsorptions follow a pseudo-second-order adsorption kinetic and monolayer Langmuir adsorption isotherm. The maximal adsorption capacities of CNF-GnP aerogels for MB and CR are 1178.5 mg g-1 and 585.3 mg g-1, respectively. CNF-GnP hybrid show a superior binary dye adsorption capacity than pristine CNF or GnP. Furthermore, nearly 80% of MB or CR can be desorbed from CNF-GNP using ethanol as the desorption agent, indicating the reusability of this hybrid material. Hence, the CNF-GnP aerogels show great promise as adsorption materials for wastewater treatment.

Efficient Hydrophobic Modification of Old Newspaper and Its Application in Paper Fiber Reinforced Composites.

Paper fibers have gained broad attention in natural fiber reinforced composites in recent years. The specific problem in preparing paper fiber reinforced composites is that paper fibers easily become flocculent after pulverization, which increases difficulties during melt-compounding with polymer matrix and results in non-uniform dispersion of paper fibers in the matrix. In this study, old newspaper (ONP) was treated with a low dosage of gaseous methyltrichlorosilane (MTCS) to solve the flocculation. The modified ONP fibers were characterized by Scanning Electron Microscope (SEM), Fourier Transform Infrared Spectroscopy (FTIR), and Thermogravimetric Analysis (TG). Then the modified ONP fibers and high-density polyethylene (HDPE) were extruded and pelletized to prepare ONP/HDPE composites via injection molding. Maleic anhydride-grafted polyethylene (MAPE) was added to enhance the interfacial bonding performance with the ultimate purpose of improving the mechanical strength of the composites. The mechanical properties such as tensile, flexural, and impact strength and the water absorption properties of the composite were tested. The results showed that the formation of hydrogen bonding between ONP fibers was effectively prevented after MTCS treatment due to the reduction of exposed -OH groups at the fiber surface. Excessive dosage of MTCS led to severe fiber degradation and dramatically reduced the aspect ratio of ONP fibers. Composites prepared with ONP fibers modified with 4% (v/w) MTCS showed the best mechanical properties due to reduced polarity between the fibers and the matrix, and the relatively long aspect ratio of treated ONP fibers. The composite with or without MAPE showed satisfactory water resistance properties. MTCS was proven to be a cheap and efficient way to pretreat old newspaper for preparing paper fiber reinforced composites.

Structural Characterization and Analysis of High-Strength Laminated Composites from Recycled Newspaper and HDPE.

Recycled newspaper (NP) shows excellent potential as a reinforcement for polymer composites. Herein, high-strength laminated composites were prepared by using NP laminas as reinforcement and high-density polyethylene (HDPE) films as matrix. Physical and mechanical properties of the laminated composites were measured. It was found that the flexural strength of the composites had a good linear relationship to its density, with R2 = 0.9853. The flexural and tensile strength of the composites at the maximum density (1.40 g/cm3) reached up to 95.6 ± 2.4 MPa and 99.4 ± 0.8 MPa, respectively. SEM results showed that NP layer inside the composite became compact at the hot pressing time of 40 min, because the melted HDPE permeated into the NP layers to bond the NP fibers. Quantitative description of the composite porosity was conducted according to the density of the composite. The 24-h water absorption of the composite was highly related to its porosity, with R2 = 0.8994. This study reveals that density of laminated composites is an important parameter, which could be used to forecast the mechanical strength, and its derived value, porosity of the composites, could be used to predict the water absorption behavior of the composite.

Cellulose I and II nanocrystals produced by sulfuric acid hydrolysis of Tetra pak cellulose I.

Polymorphism is an important factor associated with the cellulose nanomaterial properties. In this study, cellulose fibers (CFs) were efficiently isolated from waste Tetra pak packages, and cellulose I and II nanocrystals were produced by treatment of CFs with 64% sulfuric acid and controlling the reaction time from 15 to 30 min. Cellulose I (CI) was partially converted to cellulose II (CII) within 15 min and the resulting cellulose nanocrystal product (i.e. CNC15) contained 93.2% CII. Further extending the hydrolysis time decreased the CII content of CNC20 to 25.5% and CNC30 was completely CI without CII. CNC15 (285.1 ±â€¯120.7 nm long, 50.6 ±â€¯16.5 nm wide, 0.64 at% sulfur) was much thicker, slightly longer, less thermal stable and contained more sulfate groups than CNC30 (207.2 ±â€¯77.8 nm long, 23.2 ±â€¯7.8 nm wide, 0.34 at% sulfur). CNCs with controllable allomorph may have potentially diverse applications.

Isolation of cellulose nanocrystals from medium density fiberboards.

Cellulose fibers have been successfully isolated from medium density fiberboards (MDFs) by sodium chlorite oxidation-potassium hydroxide (NaClO2-KOH) leaching process, at 37.6% yield, comparable to the 39.3% and 37.3% cellulose fibers from eucalyptus and eucalyptus with 12% cured urea-formaldehyde (UF) resin, respectively. At the same sulfuric acid hydrolysis conditions (65% H2SO4, 60°C and 30min), MDF cellulose nanocrystals (CNCs) were produced at 27.5% yield, similar to 27.4% of CNC yield from eucalyptus with UF resin, but less than 31.2% yield from eucalyptus. MDF CNCs were slightly thicker in lateral dimension (16.8±8.6nm), less crystalline (59% CrI), and surface esterificated (0.045mmol/g sulfate/CNC) than eucalyptus CNCs (11.6±3.9nm, 75% CrI, 0.060mmol/g) and CNCs from eucalyptus with UF resin (14.9±9.1nm, 65% CrI, 0.046mmol/g). All CNCs were free of UF resin and thermal stable. The residual resin in cellulose pulps hydrolyzed completely during the sulfuric acid treatment and contributed to the unique properties of CNCs. Therefore, CNCs derived from MDF are comparable to CNC from wood and promising for expanded applications.