Cellulose and Cellulose Derivatives

Cellulose acetate butyrate (CAB) is a possible candidate, being a raw material derived from renewable resources, to replace fossil-based materials. This is due to its thermoplastic properties and the relative ease with which it could be implemented within the existing industry. With a significant amount of variation in CAB on the market today, a knowledge gap has been identified regarding the understanding of the polymer structural arrangement in films. This relates to the underlying mechanisms that regulate CAB film material properties, insights that are important in product development. In this study, commercially available CAB was investigated with XRD, SEM, AFM, and TOPEM DSC in order to obtain physicochemical information related to its micro-structural features in solvent-cast films. The film-forming ability relates mostly to the number of hydroxyl groups, and the semi-crystallinity of the films depends on the type and position of the side groups along the cellulose backbone. The appearance of signs of possible cholesteric ordering in the films could be connected to higher amounts of hydroxyl groups along the backbone that disturb the helix arrangement, while the overall order was primarily related to the butyrate substitution and secondarily related to the molecular weight of the particular CAB studied. Cold crystallization was also observed in one CAB sample. Full article

With the increasing importance of environmental protection, high-performance biopolymer films have received considerable attention as effective alternatives to petroleum-based polymer films. In this study, we developed hydrophobic regenerated cellulose (RC) films with good barrier properties through a simple gas–solid reaction via the chemical vapor deposition of alkyltrichlorosilane. RC films were employed to construct a biodegradable, free-standing substrate matrix, and methyltrichlorosilane (MTS) was used as a hydrophobic coating material to control the wettability and improve the barrier properties of the final films. MTS readily coupled with hydroxyl groups on the RC surface through a condensation reaction. We demonstrated that the MTS-modified RC (MTS/RC) films were optically transparent, mechanically strong, and hydrophobic. In particular, the obtained MTS/RC films exhibited a low oxygen transmission rate of 3 cm³/m² per day and a low water vapor transmission rate of 41 g/m² per day, which are superior to those of other hydrophobic biopolymer films. Full article

Innovative and sustainable all-cellulose composites (ACCs) can be obtained by partial dissolution of cellulosic fibers and regeneration of the dissolved fraction. Among cellulose solvents, sodium hydroxide/urea solutions are recognized as promising low-environmental impact systems. In this work, filter paper (FP) was dissolved with a 7 wt% NaOH/12 wt% urea aqueous solution, kept at −18 °C for different time intervals, regenerated with distilled water and finally dried under different conditions. The developed films were characterized in terms of morphology, porosity, optical properties, crystalline structure, hydration and mechanical properties. The porosity of the composites decreased with dissolution time due to the progressive filling of voids as the cellulosic fibers’ surface skin layer was dissolved and regenerated. Samples treated for 4 h showed the minimum values of porosity and opacity, high hydration and a substantial change from cellulose I to cellulose II. Hot pressing during drying led to relevant improvements in ACCs stiffness and strength values. Full article

This paper presents a strategy to convert hydrophilic cellulose nanofibrils (CNF) into a highly cross-linked hydrophobic network with inorganic nanoparticles to develop a gel ink suitable for gel 3D printing. The CNF were chemically modified initially through a single-electron transfer-living radical polymerization (SET-LRP) of stearyl acrylate (SA) in the presence of the surface-modified cobalt iron oxide (CoFe₂O₄, CFO) nanoparticles. The modified CFO nanoparticles provide their multifunctional properties, such as magnetic and electrochemical, to the CNF hybrid network and, at the same time, act as cross-linking agents between the nanocellulose fibrils, while the grafted poly-stearyl acrylate (PSA) introduces a strong hydrophobicity in the network. A suitable gel ink form of this CNF–PSA–CFO material for gel 3D printing was achieved together with a certain solvent. Some test structure prints were directly obtained with the CNF–PSA–CFO gel and were used to evaluate the consolidation of such 3D objects through solvent exchange and freeze-drying while also keeping the magnetic and electrochemical properties of CFO in the CNF-based composite intact. The pristine CNF and CFO particles and the CNF–PSA–CFO were characterized by FTIR, SEM, XPS, TGA, VSM, and CV measurements. Full article

This work aims to produce a 3D-printable bio-based filament composed of high-density polyethylene (HDPE) and chemically modified cellulose nanofibrils. Printing using HDPE as a raw material is challenging due to its massive shrinkage and warping problems. This paper presents a new method to overcome those difficulties by enhancing the mechanical properties and achieving better print quality. This was achieved using modified cellulose nanofibrils (CNFs) as fillers. Firstly, CNF was converted to a CNF-based macroinitiator through an esterification reaction, followed by a surface-initiated single-electron transfer living radical polymerization (SI-SET-LRP) of the hydrophobic monomer stearyl acrylate. Poly stearyl acrylate-grafted cellulose nanofibrils, CNF-PSAs, were synthesized, purified and characterized with ATR-FTIR, ¹³C CP-MAS NMR, FE-SEM and water contact angle measurements. A composite was successfully produced using a twin-screw extruder with a CNF-PSA content of 10 wt.%. Mechanical tests were carried out with tensile testing. An increase in the mechanical properties, up to 23% for the Young’s modulus, was observed. A morphologic analysis also revealed the good matrix/CNF compatibility, as no CNF aggregates could be observed. A reduction in the warping behavior for the composite filament compared to HDPE was assessed using a circular arc method. The 3D printing of complex objects using the CNF-PSA/HDPE filament resulted in better print quality when compared to the object printed with neat HDPE. Therefore, it could be concluded that CNF-PSA was a suitable filler for the reinforcement of HDPE, thus, rendering it suitable for 3D printing. Full article

Cellulose nanocrystals (CNCs) were successfully prepared from Sansevieria trifasciata fibers (STFs) via ammonium persulfate (APS) oxidation in this study. The influences of the APS concentration (1.1, 1.5, and 1.9 M) and oxidation temperature (60, 70, and 80 °C) on the characteristics of CNCs were studied. The resulting CNCs were characterized using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The TEM observations revealed that the rod-like CNCs possessed average length and diameter ranges of 96 to 211 nm and 5 to 13 nm, respectively, which led to an aspect ratio range of 16–19. The optimum conditions for maximum crystallinity were achieved at an oxidation temperature of 70 °C, a reaction time of 16 h, and an APS concentration of 1.5 M. All CNCs exhibited lower thermal stability compared to the STFs. The CNCs could be produced from the STFs through the APS oxidation process and showed potential as nanocomposite reinforcement materials. Full article

In this study, water vapor sorption, desorption properties and tensile mechanical properties of four cellulosic fibers, cotton (C), flax (F), viscose (V) and cellulose acetate (CA), were determined. The sorption and desorption isotherms were modeled using the Park model, which allowed an accurate fitting on the whole range of water activity. This model corresponds to a multi-sorption mode dividing in three sorption modes: Langmuir sorption, Henry’s law and water clustering. Park’s parameters were compared for the sorption and desorption isotherms for each fiber. Regardless of the fiber, differences between sorption and desorption were obtained only for the Henry sorption. The obtained sorption properties were correlated to the accessibility and the amount of sorption sites and also to the crystallinity level of the fibers. It was found that V exhibited the highest water sorption capacity due to a higher hydroxyl groups accessibility and a low amorphous fraction, followed by F, C and CA. Results from tensile tests demonstrated that F and C fibers were more rigid, more resistant and less ductile than CA and V fibers due to a difference of microstructure of the fibers. Finally, the presence of water-sorbed molecules led to a decrease in tensile modulus due to plasticization phenomenon. Full article

Nutritional food supplements and pharmaceutical products produced with vitamin K₂ as raw materials a very promising market in the global scope. The main production method of vitamin K₂ is microbial fermentation, but approximately 50% of vitamin K₂ synthesized by the main production strain Bacillus subtilis natto exists in extracellular form, which is not easy to separate and extract. In order to solve this problem, in this study, we synthesized a novel cellulose flocculant, MCC-g-LMA, by grafting reaction using microcrystalline cellulose (MCC) and lauryl methacrylate (LMA) as monomers, and ammonium persulfate as an initiator to flocculate VK₂ from the fermentation supernatant. The flocculant was characterized by Fourier transform infrared spectroscopy (FTIR), elemental analysis, and scanning electron microscopy (SEM), and the grafting reaction was successful. When the flocculant dosage was 48.0 mg/L and pH was 5.0, the flocculation rate of the MCC-g-LMA on the fermentation supernatant reached 85.3%, and the enrichment rate of VK₂ reached 90.0%. Furthermore, we explored the flocculation mechanism of VK₂ by the MCC-g-LMA and speculated that the flocculation mechanism mainly included adsorption bridging, hydrophobic association and net trapping and sweep effect. In this study, the extraction method for trace high-value biological products in the fermentation supernatant was improved, which provided a method and theoretical basis for the efficient separation and purification of VK₂ and other terpenoids. Full article

Cellulose has attracted considerable attention as the most promising potential candidate raw material for the production of bio-based polymeric materials. In the last decade, significant progress has been made in the production of biopolymers based on different cellulose forms. In this study, cellulose was obtained in an innovative and environmentally friendly way, using boxwood powder. Crude cellulose was obtained by treating Buxus powder with an ethanol–acetic acid–water mixture. Refined cellulose was then obtained by treatment with an acidic sodium hypochlorite solution and alkaline hydrogen peroxide solution. The novel chemistry of cellulose prepared by this method promises to be not only green, but also highly desirable, because of its lower emissions and low cost. It is crucial for the future of the global polymer industry. The refined cellulose was subjected to a high-temperature hydrothermal treatment under two temperatures and time conditions, with temperature gradients of 120, 140, and 160 °C, and time gradients of 1, 2, and 3 h. The samples were subjected to infrared and thermogravimetric analyses. The cellulose undergoes dehydration and thermal degradation reactions during the heat treatment process, and the thermal stability of the residual is enhanced, compared with that of virgin cellulose. Between 120 and 140 °C, the hydroxyl and hypomethyl groups on the surface of cellulose are shed. Groups in the amorphous region of the polymer are the first to be shed. The dehydration reaction reduces the number of free hydroxyl groups on the surface of the cellulose molecules. The dehydration reaction was accelerated by an increase in temperature. Between 140 and 160 °C, the β-(1,4)-glycosidic bond begins to slowly break and some furans are generated. The structure of cellulose undergoes reorganization during thermal treatment. The thermal stability of the modified material is greater than that of untreated cellulose. Full article

Efficient capture of particulate matter in the smoke mainstream using low-cost filter pads is important for cost-effective analysis of mainstream smoke. The Cambridge filter pad (CFP) is the standard material for the collection of particulate matter in the mainstream. In this work, we report a low-cost alternative to CFP, which is composed of a cellulose acetate fiber (CAF) interlayer and two cotton fiber (CF) layers on both sides. The CF/CAF/CF filter exhibited high affinity toward typical tobacco additives such as glycerol and glycerol triacetate. In addition, the CF/CAF/CF filter had a favorable porous structure for the trapping of particulate matter. Due to these beneficial features, the CF/CAF/CF filter exhibited improved particulate matter trapping performance. These results suggest that the as-developed CF/CAF/CF filter could be a low-cost alternative to CFP. Full article

The influences of interactions between carboxymethyl cellulose (CMC) and CMC/europium (III)–terbium (III) (CET) on the structure and properties of the resultant CMC/CET films were investigated by rheology at three stages of the film-drying process. According to the water content at different drying times, the kinetics curves during the film-drying process were drawn. Then, the rheology properties of film-forming solutions during the drying process were characterized by dynamic modulus, Han plots, zero shear complex viscosity and relaxation time. When the water content was 90%, the film contained either 0.1 or 0.2 g of CET, which had good fluidity, while the film with 0.3 g of CET was elastic-dominated. Han plots and XRD analyses showed that the interactions between the CMC and CET were not hydrogen bonds but random entanglements. The zero-shear complex viscosity and relaxation time spectrum confirmed that the entanglements enhanced as the CET content increased. Meanwhile, aggregation formed in the solution of CMC with 0.3 g of CET. When CMC-CET films with different CET additions were compared, the film with 0.2 g of CET had an even and tight sheet structure, the greatest fluorescence intensity, and superior tensile strength of 78.76 MPa. Full article

Cellulose is a renewable resource for the production of advanced carbonaceous materials for various applications. In addition to direct carbonization, attention has recently been paid to the preparation of porous carbons from liquid cellulose-based precursors. Possible pathways of cellulose conversion to a liquid state suitable for the preparation of porous carbons are summarized in this review. Hydrothermal liquefaction leading to liquid mixtures of low-molecular-weight organics is described in detail together with less common decomposition techniques (microwave or ultrasound assisted liquefaction, decomposition in a strong gravitation field). We also focus on dissolution of cellulose without decomposition, with special attention paid to dissolution of nonderivatized cellulose. For this purpose, cold alkalines, hot acids, ionic liquids, or alcohols are commonly used. Full article