Fabrication of Cellulose Film with Enhanced Mechanical Properties in Ionic Liquid 1-Allyl-3-methylimidaxolium Chloride (AmimCl)

More and more attention has been paid to environmentally friendly bio-based renewable materials as the substitution of fossil-based materials, due to the increasing environmental concerns. In this study, regenerated cellulose films with enhanced mechanical property were prepared via incorporating different plasticizers using ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as the solvent. The characteristics of the cellulose films were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), thermal analysis (TG), X-ray diffraction (XRD), ¹³C Solid-state cross-polarization/magic angle spinning nuclear magnetic resonance (CP/MAS NMR) and tensile testing. The results showed that the cellulose films exhibited a homogeneous and smooth surface structure. It was noted that the thermal stability of the regenerated cellulose film plasticized with glycerol was increased compared with other regenerated cellulose films. Furthermore, the incorporation of plasticizers dramatically strengthened the tensile strength and improved the hydrophobicity of cellulose films, as compared to the control sample. Therefore, these notable results exhibited the potential utilization in producing environmentally friendly cellulose films with high performance properties.     

Dispersion Process and Effect of Oleic Acid on Properties of Cellulose Sulfate- Oleic Acid Composite Film

The cellulose sulfate (CS) is a newly developed cellulose derivative. The work aimed to investigate the effect of oleic acid (OA) content on properties of CS-OA film. The process of oleic acid dispersion into film was described to evaluate its effect on the properties of the film. Among the formulations evaluated, the OA addition decreased the solubility and water vapor permeability of the CS-OA film. The surface contact angle changed from 64.2° to 94.0° by increasing CS/OA ratio from 1:0 to 1:0.25 (w/w). The TS increased with OA content below 15% and decreased with OA over 15%, but the ε decreased with higher OA content. The micro-cracking matrices and micro pores in the film indicated the condense structure of the film destroyed by the incorporation of oleic acid. No chemical interaction between the OA and CS was observed in the XRD and FTIR spectrum. Film formulation containing 2% (w/w) CS, 0.3% (w/w) glycerol and 0.3% (w/w) OA, showed good properties of mechanic, barrier to moisture and homogeneity.     

Comparison of Mechanical and End-Use Properties of Grey and Dyed Cellulose and Cellulose/Protein Woven Fabrics

The behaviour of textile products made from different fibres during finishing has been investigated by many scientists, but these investigations have usually been performed with cotton or synthetic yarns and fabrics. However, the properties of raw materials such as linen and hemp (other cellulose fibres) and linen/silk (cellulose/protein fibres) have rarely been investigated. The aim of the study was to investigate and compare the mechanical (breaking force and elongation at break) and end-use (colour fastness to artificial light, area density, and abrasion resistance) properties of cellulose and cellulose/protein woven fabrics. For all fabrics, ΔE was smaller than three, which is generally imperceptible to the human eye. Flax demonstrated the best dyeability, and hemp demonstrated the poorest dyeability, comparing all the tested fabrics. The colour properties of fabrics were greatly influenced by the washing procedure, and even different fabric components of different weaves lost their colours in different ways. Flax fibres were more crystalline than hemp, and those fibres were more amorphous, which decreased the crystallinity index of flax in flax/silk blended fabric. Unwashed flax fabric was more resistant to artificial light than flax/silk or hemp fabrics. Finishing had a great influence on the abrasion resistance of fabrics. The yarn fibre composition and the finishing process for fabrics both influenced the mechanical (breaking force and elongation at break) and end-use (area density and abrasion resistance) properties of grey and finished fabrics woven from yarns made of different fibres.     

Effect of Psyllium Husk Addition on the Structural and Physical Properties of Biodegradable Thermoplastic Starch Film

The research subject was the analysis of the microstructure, barrier properties, and mechanical resistance of the psyllium husk (PH)-modified thermoplastic starch films. The tensile tests under various static loading conditions were not performed by researchers for this type of material before and are essential for a more precise assessment of the material’s behavior under the conditions of its subsequent use. The film samples were manufactured by the casting method. PH addition improved starch gelatinization and caused a decrease in failure strain by 86% and an increase in failure stress by 48% compared to pure films. Fourier transform infrared spectroscopy results showed the formation of additional hydrogen bonds between polysaccharides in starch and PH. An increase in the number of hydrophilic groups in the modified films resulted in a faster contact angle decrease (27.4% compared to 12.8% for pure ones within the first 5 s); however, it increased the energy of water binding and surface complexity. The modified films showed the opacity at 600 nm, 43% higher than in the pure starch film, and lower transmittance, suggesting effectively improving barrier properties to UV light, a potent lipid-oxidizing agent in food systems.     

Nanocrystalline Cellulose from Microcrystalline Cellulose of Date Palm Fibers as a Promising Candidate for Bio-Nanocomposites: Isolation and Characterization

Date palm fiber (Phoenix dactylifera L.) is a natural biopolymer rich in lignocellulosic components. Its high cellulose content lends them to the extraction of tiny particles like microcrystalline cellulose (MCC) and nanocrystalline cellulose (NCC). These cellulose-derived small size particles can be used as an alternative biomaterial in wide fields of application due to their renewability and sustainability. In the present work, NCC (A) and NCC (B) were isolated from date palm MCC at 60 min and 90 min hydrolysis times, respectively. The isolated NCC product was subjected to characterization to study their properties differences. With the hydrolysis treatment, the yields of produced NCC could be attained at between 22% and 25%. The infrared-ray functional analysis also revealed the isolated NCC possessed a highly exposed cellulose compartment with minimized lignoresidues of lignin and hemicellulose. From morphology evaluation, the nanoparticles’ size was decreased gradually from NCC (A) (7.51 nm width, 139.91 nm length) to NCC (B) (4.34 nm width, 111.51 nm length) as a result of fragmentation into cellulose fibrils. The crystallinity index was found increasing from NCC (A) to NCC (B). With 90 min hydrolysis time, NCC (B) showed the highest crystallinity index of 71% due to its great cellulose rigidity. For thermal analysis, NCC (B) also exhibited stable heat resistance, in associating with its highly crystalline cellulose structure. In conclusion, the NCC isolated from date palm MCC would be a promising biomaterial for various applications such as biomedical and food packaging applications.     

Mechanical,Microstructure and Surface Characterizations of Carbon Fibers Prepared from Cellulose after Liquefying and Curing

In this study, Cellulose-based carbon fibers (CBCFs) were prepared from cellulose after phenol liquefaction and curing. The characteristics and properties of CBCFs were examined by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The results showed that, with increasing carbonization temperature, the L_a, L_c, and L_c/d₍₀₀₂₎ of CBCFs increased gradually, whereas the degree of disorder R decreased. The –OH, –CH₂–, –O–C– and phenyl group characteristic absorption peaks of CBCFs reduced gradually. The cross-linked structure of CBCFs was converted into a graphite structure with a six-ring carbon network during carbonization. The surface of CBCFs were mainly comprised of C–C, C–O, and C=O. The tensile strength, carbonization yield and carbon content of CBCFs obtained at 1000 °C were 1015 MPa, 52%, and 95.04%, respectively.     

Methylcellulose–Cellulose Nanocrystal Composites for Optomechanically Tunable Hydrogels and Fibers

Chemical modification of cellulose offers routes for structurally and functionally diverse biopolymer derivatives for numerous industrial applications. Among cellulose derivatives, cellulose ethers have found extensive use, such as emulsifiers, in food industries and biotechnology. Methylcellulose, one of the simplest cellulose derivatives, has been utilized for biomedical, construction materials and cell culture applications. Its improved water solubility, thermoresponsive gelation, and the ability to act as a matrix for various dopants also offer routes for cellulose-based functional materials. There has been a renewed interest in understanding the structural, mechanical, and optical properties of methylcellulose and its composites. This review focuses on the recent development in optically and mechanically tunable hydrogels derived from methylcellulose and methylcellulose–cellulose nanocrystal composites. We further discuss the application of the gels for preparing highly ductile and strong fibers. Finally, the emerging application of methylcellulose-based fibers as optical fibers and their application potentials are discussed.     

Conductive Regenerated Cellulose Fibers for Multi-Functional Composites: Mechanical and Structural Investigation

Regenerated cellulose fibers coated with copper via electroless plating process are investigated for their mechanical properties, molecular structure changes, and suitability for use in sensing applications. Mechanical properties are evaluated in terms of tensile stiffness and strength of fiber tows before, during and after the plating process. The effect of the treatment on the molecular structure of fibers is investigated by measuring their thermal stability with differential scanning calorimetry and obtaining Raman spectra of fibers at different stages of the treatment. Results show that the last stage in the electroless process (the plating step) is the most detrimental, causing changes in fibers’ properties. Fibers seem to lose their structural integrity and develop surface defects that result in a substantial loss in their mechanical strength. However, repeating the process more than once or elongating the residence time in the plating bath does not show a further negative effect on the strength but contributes to the increase in the copper coating thickness, and, subsequently, the final stiffness of the tows. Monitoring the changes in resistance values with applied strain on a model composite made of these conductive tows show an excellent correlation between the increase in strain and increase in electrical resistance. These results indicate that these fibers show potential when combined with conventional composites of glass or carbon fibers as structure monitoring devices without largely affecting their mechanical performance.     

Hydrogen-Bonding-Aided Fabrication of Wood Derived Cellulose Scaffold/Aramid Nanofiber into High-Performance Bulk Material

Preparing a lightweight yet high-strength bio-based structural material with sustainability and recyclability is highly desirable in advanced applications for architecture, new energy vehicles and spacecraft. In this study, we combined cellulose scaffold and aramid nanofiber (ANF) into a high-performance bulk material. Densification of cellulose microfibers containing ANF and hydrogen bonding between cellulose microfibers and ANF played a crucial role in enhanced physical and mechanical properties of the hybrid material. The prepared material showed excellent tensile strength (341.7 MPa vs. 57.0 MPa for natural wood), toughness (4.4 MJ/m³ vs. 0.4 MJ/m³ for natural wood) and Young’s modulus (24.7 GPa vs. 7.2 GPa for natural wood). Furthermore, due to low density, this material exhibited a superior specific strength of 285 MPa·cm³·g⁻¹, which is remarkably higher than some traditional building materials, such as concrete, alloys. In addition, the cellulose scaffold was infiltrated with ANFs, which also improved the thermal stability of the hybrid material. The facile and top-down process is effective and scalable, and also allows one to fully utilize cellulose scaffolds to fabricate all kinds of advanced bio-based materials.     

Processing and Characterization of Cellulose Nanocrystals/Polylactic Acid Nanocomposite Films

The focus of this study is to examine the effect of cellulose nanocrystals (CNC) on the properties of polylactic acid (PLA) films. The films are fabricated via melt compounding and melt fiber spinning followed by compression molding. Film fracture morphology, thermal properties, crystallization behavior, thermo-mechanical behavior, and mechanical behavior were determined as a function of CNC content using scanning electron microscopy, differential scanning calorimetry, X-ray diffraction, dynamic mechanical analysis, and tensile testing. Film crystallinity increases with increasing CNC content indicating CNC act as nucleating agents, promoting crystallization. Furthermore, the addition of CNC increased the film storage modulus and slightly broadened the glass transition region.     

Analysis and Optimization of Mechanical Properties of Laser-Sintered Cellulose/PLA Mixture

This studied aimed at improving the mechanical properties for a new biopolymer feedstock using laser-sintering technology, especially when its laser-sintered parts are intended to be applied in the industrial and medical fields. Process parameter optimization and thermal post-processing are two approaches proposed in this work to improve the mechanical properties of laser-sintered 10 wt % cellulose-polylactic acid (10%-CPLA) parts. Laser-sintering experiments using 2³ full factorial design method were conducted to assess the effects of process parameters on parts’ mechanical properties. A simulation of laser-energy distribution was carried out using Matlab to evaluate the experimental results. The characterization of mechanical properties, crystallinity, microstructure, and porosity of laser-sintered 10%-CPLA parts after thermal post-processing of different annealing temperatures was performed to analyze the influence of thermal post-processing on part properties. Image analysis of fracture surfaces was used to obtain the porosity of laser-sintered 10%-CPLA parts. Results showed that the optimized process parameters for mechanical properties of laser-sintered 10%-CPLA parts were laser power 27 W, scan speed 1600 mm/s, and scan spacing 0.1 mm. Thermal post-processing at 110 °C produced best properties for laser-sintered 10%-CPLA parts.     

Mechanical and Air Permeability Performance of Novel Biobased Materials from Fungal Hyphae and Cellulose Fibers

Novel biobased materials from fungal hyphae and cellulose fibers have been proposed to address the increasing demand for natural materials in personal protective equipment (PPE). Materials containing commercially available kraft fibers (KF), laboratory-made highly fibrillated hemp fibers (HF) and fungal fibers (FF) obtained from fruiting bodies of lignicolous basidiomycetes growing in nature were prepared using paper production techniques and evaluated for their mechanical and air permeability properties. SEM and microscopy revealed the network structure of materials. The tensile index of materials was in the range of 8–60 Nm/g and air permeability ranged from 32–23,990 mL/min, depending on the composition of materials. HF was the key component for strength; however, the addition of FF to compositions resulted in higher air permeability. Chemical composition analysis (Fourier-transform infrared spectroscopy) revealed the presence of natural polysaccharides, mainly cellulose and chitin, as well as the appropriate elemental distribution of components C, H and N. Biodegradation potential was proven by a 30-day-long composting in substrate, which resulted in an 8–62% drop in the C/N ratio. Conclusions were drawn about the appropriateness of fungal hyphae for use in papermaking-like technologies together with cellulose fibers. Developed materials can be considered as an alternative to synthetic melt and spun-blown materials for PPE.     

Development of Chitosan/Bacterial Cellulose Composite Films Containing Nanodiamonds as a Potential Flexible Platform for Wound Dressing

Chitosan/bacterial cellulose composite films containing diamond nanoparticles (NDs) with potential application as wound dressing are introduced. Microstructural studies show that NDs are uniformly dispersed in the matrix, although slight agglomeration at concentrations above 2 wt % is seen. Fourier transform infrared spectroscopy reveals formation of hydrogen bonds between NDs and the polymer matrix. X-ray diffraction analysis indicates reduced crystallinity of the polymer matrix in the presence of NDs. Approximately 3.5-fold increase in the elastic modulus of the composite film is obtained by the addition of 2 wt % NDs. The results of colorimetric analysis show that the composite films are transparent but turn to gray-like and semitransparent at high ND concentrations. Additionally, a decrease in highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) gap is also seen, which results in a red shift and higher absorption intensity towards the visible region. Mitochondrial activity assay using L929 fibroblast cells shows that the nanocomposite films are biocompatible (>90%) after 24 h incubation. Multiple lamellapodia and cell-cell interaction are shown. The results suggest that the developed films can potentially be used as a flexible platform for wound dressing.     

Comparison of Cellulose Dissolution Behavior by Alkaline and Sulfuric Acid Solvents and Their Films’ Physical Properties

Three alkaline mixtures (NaOH/thiourea, NaOH/urea/thiourea, NaOH/urea/ZnO) and sulfuric acid were used at low temperatures as cellulose solvents, and their cellulose solubility and films’ physical properties for bleached chemical wood pulps and cotton linter were compared. Their degree of polymerization (DP) was controlled to 600–800 before dissolution. Among the alkaline solvents, NaOH/urea/ZnO gave the film the highest tensile strength and stretch. When compared to sulfuric acid, NaOH/urea/ZnO gave lower strength properties but higher crystallinity indices in the films. While alkaline solvents could not dissolve the high DP cellulose (DP ~ 2000), sulfuric acid could dissolve the high DP cellulose at below zero Celsius temperature, and the strength properties of the films were not much different from that of the low DP one. It appeared that the low-temperature sulfuric acid treatment did away with the cellulose’s DP controlling stage; it decreased cellulose DP very quickly for the high-DP cellulose at the initial stage, and as soon as the cellulose DP reached a DP low enough for dissolution, it began to dissolve the cellulose to result in stable cellulose solution.     

Synthesis and Physicochemical Properties of Poly(vinyl) Alcohol Nanocomposites Reinforced with Nanocrystalline Cellulose from Tea (Camellia sinensis) Waste

The purpose of this study was to utilize cellulose from tea waste as nanocrystalline cellulose (NCC), which is used as a filler in poly(vinyl) alcohol (PVA) nanocomposites. To obtain the NCC, a chemical process was conducted in the form of alkali treatment, followed by bleaching and hydrolysis. Nanocomposites were formed by mixing PVA with various NCC suspensions. With chemical treatment, lignin and hemicellulose can be removed from the tea waste to obtain NCC. This can be seen in the functional groups of cellulose and the increase in crystallinity. The NCC had a mean diameter of 6.99 ± 0.50 nm. Furthermore, the addition of NCC to the PVA nanocomposite influenced the properties of the nanocomposites. This can be seen in the general increase in opacity value, thermal and mechanical properties, and crystallinity, as well as the decrease in the value of the swelling ratio after adding NCC. This study has revealed that NCC from tea waste can be used to improve the physicochemical properties of PVA film.     

Iso- and Anisotropic Etching of Micro Nanofibrillated Cellulose Films by Sequential Oxygen and Nitrogen Gas Plasma Exposure for Tunable Wettability on Crystalline and Amorphous Regions

The surface of cellulose films, obtained from micro nanofibrillated cellulose produced with different enzymatic pretreatment digestion times of refined pulp, was exposed to gas plasma, resulting in a range of surface chemical and morphological changes affecting the mechanical and surface interactional properties. The action of separate and dual exposure to oxygen and nitrogen cold dielectric barrier discharge plasma was studied with respect to the generation of roughness (confocal laser and atomic force microscopy), nanostructural and chemical changes on the cellulose film surface, and their combined effect on wettability. Elemental analysis showed that with longer enzymatic pretreatment time the wetting response was sensitive to the chemical and morphological changes induced by both plasma gases, but distinctly oxygen plasma was seen to induce much greater morphological change while nitrogen plasma contributed more to chemical modification of the film surface. In this novel study, it is shown that exposure to oxygen plasma, subsequently followed by exposure to nitrogen plasma, leads first to an increase in wetting, and second to more hydrophobic behaviour, thus improving, for example, suitability for printing using polar functional inks or providing film barrier properties, respectively.     

Modern Biodegradable Plastics—Processing and Properties Part II

Four different plastics were tested: potato starch based plastic (TPS-P)–BIOPLAST GF 106/02; corn starch based plastic (TPS-C)–BioComp BF 01HP; polylactic acid (polylactide) plastic (PLA)—BioComp BF 7210 and low density polyethylene, trade name Malen E FABS 23-D022; as a petrochemical reference sample. Using the blown film extrusion method and various screw rotational speeds, films were obtained and tested, as a result of which the following were determined: breaking stress, strain at break, static and dynamic friction coefficient of film in longitudinal and transverse direction, puncture resistance and strain at break, color, brightness and gloss of film, surface roughness, barrier properties and microstructure. The biodegradable plastics tested are characterized by comparable or even better mechanical strength than petrochemical polyethylene for the range of film blowing processing parameters used here. The effect of the screw rotational speed on the mechanical characteristics of the films obtained was also demonstrated. With the increase in the screw rotational speed, the decrease of barrier properties was also observed. No correlation between roughness and permeability of gases and water vapor was shown. It was indicated that biodegradable plastics might be competitive for conventional petrochemical materials used in film blowing niche applications where cost, recyclability, optical and water vapor barrier properties are not critical.     

Effect of Layer and Film Thickness and Temperature on the Mechanical Property of Micro- and Nano-Layered PC/PMMA Films Subjected to Thermal Aging

Multilayered polymer films with biomimicking, layered structures have unique microstructures and many potential applications. However, a major limitation of polymer films is the deterioration of mechanical properties in working environments. To facilitate the design and development of multilayered polymer films, the impact of thermal aging on the mechanical behavior of micro- and nano-layered polymer films has been investigated experimentally. The composition of the polymer films that have been studied is 50 vol% polycarbonate (PC) and 50 vol% poly(methyl methacrylate) (PMMA). The current study focuses on the effect of film and layer thickness and temperature on the mechanical properties of the materials subjected to thermal aging. To study the effect of film and layer thickness, films with the same thickness, but various layer thicknesses, and films with the same layer thickness, but various film thicknesses, were thermally aged at 100 °C in a constant temperature oven for up to six weeks. The results show that as the layer thickness decreases to 31 nm, the film has a higher stiffness and strength, and the trend of the mechanical properties is relatively stable over aging. The ductility of all of the films decreases with aging time. To study the effect of temperature, the films with 4,096 layers (31 nm thick for each layer) were aged at 100 °C, 115 °C and 125 °C for up to four weeks. While the 100 °C aging results in a slight increase of the stiffness and strength of the films, the higher aging temperature caused a decrease of the stiffness and strength of the films. The ductility decreases with the aging time for all of the temperatures. The films become more brittle for higher aging temperatures.     

Production and Characterization of a New Bacterial Cellulose/Poly(Vinyl Alcohol) Nanocomposite

Bacterial cellulose (BC) is characterized for its high water holding capacity, high crystallinity, an ultrafine fiber network and high tensile strength. This work demonstrates the production of a new interpenetrated polymer network nanocomposite obtained through the incorporation of poly(vinyl alcohol) (PVA) on the BC matrix and evaluates the effect of oven drying on the morphological, mechanical and mass transfer properties of the composite membranes. Both the addition of PVA and oven drying induce the appearance of larger pores (circa 1–3 µm in average diameter) in dried BC/PVA membranes. Both types of treatments also affect the permeability of the composite, as assessed by the diffusion coefficients of polyethylene glycol (PEG) molecules (900, 8,000, 35,000 and 100,000 Da) across the membranes. Finally, the Young’s modulus of dry pristine BC decreases following PVA incorporation, resulting in a change from 3.5 GPa to 1 GPa and a five-fold loss in tensile strength.     

A Comparative Density Functional Theory Study of Hydrogen Storage in Cellulose and Chitosan Functionalized by Transition Metals (Ti,Mg, and Nb)

The focus of this work is hydrogen storage in pristine cellulose, chitosan, and cellulose. Chitosan doped with magnesium, titanium, and niobium is analyzed using spin unrestricted plane-wave density functional theory implemented in the Dmol³ module. The results of this study demonstrate that hydrogen interaction with pure cellulose and chitosan occurred in the gas phase, with an adsorption energy of Eb = 0.095 eV and 0.090 eV for cellulose and chitosan, respectively. Additionally, their chemical stability was determined as Eb= 4.63 eV and Eb = 4.720 eV for pure cellulose and chitosan, respectively, by evaluating their band gap. Furthermore, the presence of magnesium, titanium, and niobium on cellulose and chitosan implied the transfer of an electron from metal to cellulose and chitosan. Moreover, our calculations predict that cellulose doped with niobium is the most favorable medium where 6H₂ molecules are stored compared with molecules stored in niobium-doped chitosan with T_max = 818 K to release all H₂ molecules. Furthermore, our findings showed that titanium-doped cellulose has a storage capacity of five H₂ molecules, compared to a storage capacity of four H₂ molecules in titanium-doped chitosan. However, magnesium-doped cellulose and chitosan have insufficient hydrogen storage capacity, with only two H₂ molecules physisorbed in the gas phase. These results suggest that niobium-doped cellulose and chitosan may play a crucial role in the search for efficient and inexpensive hydrogen storage media.