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.

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 %.

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.

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.

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.

Enhanced fluoride removal behaviour and mechanism by dicalcium phosphate from aqueous solution.

Dicalcium phosphate was prepared by ethylenediaminetetraacetic acid as a calcium chelating agent, and further explored to remove the fluoride ions from aqueous solution. The as-prepared samples main existed in the monetite phase from the result of XRD. The dried sample consisted of small nanoparticles and displayed irregular particles with a size of ca. 3 µm due to the agglomeration. The fluoride removal ability was evaluated by batch adsorption experiments. The as-prepared adsorbent exhibited the enhanced fluoride removal behaviour with the maximum adsorption capacity of 66.72 mg/g from the Langmuir isotherm model, which was higher than that of other previously reported calcium phosphate. The adsorbent could be utilized in the wide pH range of 3-10. The adsorption kinetics could be better described by the pseudo-second-order model than first-second-order model. The co-existing anions had a negligible influence on the fluoride adsorption. The investigation of adsorption mechanism suggested that the chemical reaction and/or dissolution - precipitation mechanism should be dominant in the fluoride adsorption process, accompanying with electronic interaction and ions exchange, which enhanced the fluoride removal performance.

Sorption of Cu2+ and Zn2+ by natural biomaterial: duck feather.

Feather fibers were modified by treatment with 5% tannic acid (TA) solution. Kinetics of the modification was investigated as a function of the reaction time. The maximum loading of TA on feather reached 8.3% after being treated by TA for 9 h. The adsorption of metal cations (Cu2+, Zn2+) by unmodified and TA-modified feather fibers was investigated as a function of fiber weight gain, temperature, and pH of the metal solution. The adsorption was enhanced at alkaline pH and ambient temperature and increased with the weight gain of TA. The maximum uptake of metal cations (Cu2+, 0.77 mmol/g; Zn2+, 0.95 mmol/g) was obtained by TA-modified feather at weight gain: 8.3%, pH 11, while at the acidic pH, the adsorption of metal cations by either unmodified or TA-modified feather was negligible. The influence of anions on the adsorption of metal cations was also studied. The uptake of Cu2+ from chloride was higher and faster than that from nitrate. Desorption of the metals was performed at acidic pH 2.5 for 48 h. The feather-TA-metal complexes exhibited higher stability for metal cations than the feather-metal complexes. All these experiments reveal that TA-modified feather fibers have good adsorption to metal cations and can be used as metal adsorbent in wastewater treatment.

Biomimetic soy protein nanocomposites with calcium carbonate crystalline arrays for use as wood adhesive.

Despite the biodegradability, non-toxicity, and renewability, commercially available soy protein-based adhesives still have not been widely adopted by industry, partially due to their disappointing performances, i.e., low glue strength in the dry state and no glue strength in the wet state. In this study, biomimetic soy protein/CaCO(3) hybrid wood glue was devised and an attempt made to improve the adhesion strength. The structure and morphology of the adhesive and its fracture bonding interface and adhesion strength were investigated. Results showed that the compact rivets or interlocking links, and ion crosslinking of calcium, carbonate, hydroxyl ions in the adhesive greatly improving the water-resistance and bonding strength of soy protein adhesives. Glue strength of soy protein hybrid adhesive was higher than 6 MPa even after three water-immersion cycles. This green and sustainable proteinous hybrid adhesive, with high glue strength and good water-resistance, is a good substitute for formaldehyde wood glues.