Nanocellulose was extracted from short bast fibers, from hemp (Cannabis sativa L.) plants harvested at seed maturity, non-retted, and mechanically decorticated in a defibering apparatus, giving non-aligned fibers. A chemical pretreatment with NaOH and HCl allowed the removal of most of the non-cellulosic components of the fibers. No bleaching was performed. The chemically pretreated fibers were then refined in a beater and treated with a cellulase enzyme, followed by mechanical defibrillation in an ultrafine friction grinder. The fibers were characterized by microscopy, infrared spectroscopy, thermogravimetric analysis and X-ray diffraction after each step of the process to understand the evolution of their morphology and composition. The obtained nanocellulose suspension was composed of short nanofibrils with widths of 5-12 nm, stacks of nanofibrils with widths of 20-200 nm, and some larger fibers. The crystallinity index was found to increase from 74% for the raw fibers to 80% for the nanocellulose. The nanocellulose retained a yellowish color, indicating the presence of some residual lignin. The properties of the nanopaper prepared with the hemp nanocellulose were similar to those of nanopapers prepared with wood pulp-derived rod-like nanofibrils.
Hydrogels are an attractive system for a myriad of applications. While most hydrogels are usually formed from synthetic materials, lignocellulosic biomass appears as a sustainable alternative for hydrogel development. The valorization of biomass, especially the non-woody biomass to meet the growing demand of the substitution of synthetics and to leverage its benefits for cellulose hydrogel fabrication is attractive. This review aims to present an overview of advances in hydrogel development from non-woody biomass, especially using native cellulose. The review will cover the overall process from cellulose depolymerization, dissolution to crosslinking reaction and the related mechanisms where known. Hydrogel design is heavily affected by the cellulose solubility, crosslinking method and the related processing conditions apart from biomass type and cellulose purity. Hence, the important parameters for rational designs of hydrogels with desired properties, particularly porosity, transparency and swelling characteristics will be discussed. Current challenges and future perspectives will also be highlighted.
The use of chemical modification of cellulosic fibre is applied in order to increase the hydrophobicity, hence improving the compatibility between the fibre and matrix bonding. In this study, the effect of propionic anhydride modification of kenaf fibre was investigated to determine the role of bionanocarbon from oil palm shell agricultural wastes in the improvement of the functional properties of bionanocomposites. The vinyl esters reinforced with unmodified and propionic anhydride modified kenaf fibres bio nanocomposites were prepared using 0, 1, 3, 5 wt% of bio-nanocarbon. Characterisation of the fabricated bionanocomposite was carried out using FESEM, TEM, FT-IR and TGA to investigate the morphological analysis, surface properties, functional and thermal analyses, respectively. Mechanical performance of bionanocomposites was evaluated according to standard methods. The chemical modification of cellulosic fibre with the incorporation of bionanocarbon in the matrix exhibited high enhancement of the tensile, flexural, and impact strengths, for approximately 63.91%, 49.61% and 54.82%, respectively. The morphological, structural and functional analyses revealed that better compatibility of the modified fibre-matrix interaction was achieved at 3% bionanocarbon loading, which indicated improved properties of the bionanocomposite. The nanocomposites exhibited high degradation temperature which signified good thermal stability properties. The improved properties of the bionanocomposite were attributed to the effect of the surface modification and bionanocarbon enhancement of the fibre-matrix networks.
Vitamin D deficiency is now a global health problem; despite several drug delivery systems for carrying vitamin D due to low bioavailability and loss bioactivity. Developing a new drug delivery system to deliver vitamin D3 is a strong incentive in the current study. Hence, an implantable drug delivery system (IDDS) was developed from the electrospun cellulose acetate (CA) and ε-polycaprolactone (PCL) nanofibrous membrane, in which the core of implants consists of vitamin D3-loaded CA nanofiber (CAVD) and enclosed in a thin layer of the PCL membrane (CAVD/PCL). CA nanofibrous mat loaded with vitamin D3 at the concentrations of 6, 12, and 20% (w/w) of vitamin D3 were produced using electrospinning. The smooth and bead-free fibers with diameters ranged from 324 to 428 nm were obtained. The fiber diameters increased with an increase in vitamin D3 content. The controlled drug release profile was observed over 30-days, which fit with the zero-order model (R2 > 0.96) in the first stage. The mechanical properties of IDDS were improved. Young's modulus and tensile strength of CAVD/PCL (dry) were161 ± 14 and 13.07 ± 2.5 MPa, respectively. CA and PCL nanofibers are non-cytotoxic based on the results of the in-vitro cytotoxicity studies. This study can further broaden in-vivo study and provide a reference for developing a new IDDS to carry vitamin D3 in the future.
Cellulose nanofibers (CNF) isolated from plant biomass have attracted considerable interests in polymer engineering. The limitations associated with CNF-based nanocomposites are often linked to the time-consuming preparation methods and lack of desired surface functionalities. Herein, we demonstrate the feasibility of preparing a multifunctional CNF-zinc oxide (CNF-ZnO) nanocomposite with dual antibacterial and reinforcing properties via a facile and efficient ultrasound route. We characterized and examined the antibacterial and mechanical reinforcement performances of our ultrasonically induced nanocomposite. Based on our electron microscopy analyses, the ZnO deposited onto the nanofibrous network had a flake-like morphology with particle sizes ranging between 21 to 34 nm. pH levels between 8-10 led to the formation of ultrafine ZnO particles with a uniform size distribution. The resultant CNF-ZnO composite showed improved thermal stability compared to pure CNF. The composite showed potent inhibitory activities against Gram-positive (methicillin-resistant Staphylococcus aureus (MRSA)) and Gram-negative Salmonella typhi (S. typhi) bacteria. A CNF-ZnO-reinforced natural rubber (NR/CNF-ZnO) composite film, which was produced via latex mixing and casting methods, exhibited up to 42% improvement in tensile strength compared with the neat NR. The findings of this study suggest that ultrasonically-synthesized palm CNF-ZnO nanocomposites could find potential applications in the biomedical field and in the development of high strength rubber composites.
Cellulose was extracted from rice husk (RH) using an integrated delignification process using alkaline treatment and acid hydrolysis (concentrated HNO3) for lignocellulosic biomass dissolution. Cellulose yield and quality were assessed through analysis of lignocellulosic content, thermogravimetric, functional group, X-ray diffraction, and surface morphology. HNO3 treatment showed an increment (2.01-fold) in the cellulose content and some enhancement in the crystallinity of cellulose (up to 40.8%). A slight increase was observed in thermal properties from 334.6 °C to 339.3 °C. Economic analysis showed chlorine extraction produce higher cellulose recovery (58%) as compared to HNO3 (26.7%) with the total cost of operation using HNO3 was double compared to chlorine extraction. The economic feasibility of HNO3 can be improved using various progress in the pre-treatment process, chemical recycling and cellulose recovery process since adopting it is crucial for environmental sustainability.
Hydrophilic behaviour of carrageenan macroalgae biopolymer, due to hydroxyl groups, has limited its applications, especially for packaging. In this study, macroalgae were reinforced with cellulose nanofibrils (CNFs) isolated from kenaf bast fibres. The macroalgae CNF film was after that treated with silane for hydrophobicity enhancement. The wettability and functional properties of unmodified macroalgae CNF films were compared with silane-modified macroalgae CNF films. Characterisation of the unmodified and modified biopolymers films was investigated. The atomic force microscope (AFM), SEM morphology, tensile properties, water contact angle, and thermal behaviour of the biofilms showed that the incorporation of Kenaf bast CNF remarkably increased the strength, moisture resistance, and thermal stability of the macroalgae biopolymer films. Moreover, the films' modification using a silane coupling agent further enhanced the strength and thermal stability of the films apart from improved water-resistance of the biopolymer films compared to unmodified films. The morphology and AFM showed good interfacial interaction of the components of the biopolymer films. The modified biopolymer films exhibited significantly improved hydrophobic properties compared to the unmodified films due to the enhanced dispersion resulting from the silane treatment. The improved biopolymer films can potentially be utilised as packaging materials.
The degradation and mechanical properties of potential polymeric materials used for green manufacturing are significant determinants. In this study, cellulose nanofibre was prepared from Schizostachyum brachycladum bamboo and used as reinforcement in the PLA/chitosan matrix using melt extrusion and compression moulding method. The cellulose nanofibre(CNF) was isolated using supercritical carbon dioxide and high-pressure homogenisation. The isolated CNF was characterised with transmission electron microscopy (TEM), FT-IR, zeta potential and particle size analysis. The mechanical, physical, and degradation properties of the resulting biocomposite were studied with moisture content, density, thickness swelling, tensile, flexural, scanning electron microscopy, thermogravimetry, and biodegradability analysis. The TEM, FT-IR, and particle size results showed successful isolation of cellulose nanofibre using this method. The result showed that the physical, mechanical, and degradation properties of PLA/chitosan/CNF biocomposite were significantly enhanced with cellulose nanofibre. The density, thickness swelling, and moisture content increased with the addition of CNF. Also, tensile strength and modulus; flexural strength and modulus increased; while the elongation reduced. The carbon residue from the thermal degradation and the glass transition temperature of the PLA/chitosan/CNF biocomposite was observed to increase with the addition of CNF. The result showed that the biocomposite has potential for green and sustainable industrial application.
Spherical aerogels are not easily broken during use and are easier to transport and store which can be used as templates for drug delivery. This review summarizes the possible approaches for the preparation of aerogel beads and microspheres based on chitosan and cellulose, an overview to the methods of manufacturing droplets is presented, afterwards, the transition mechanisms from sol to a spherical gel are reviewed in detail followed by different drying processes to obtain spherical aerogels with porous structures. Additionally, a specific focus is given to aerogel beads and microspheres to be regarded as drug delivery carriers. Furthermore, a core/shell architecture of aerogel beads and microspheres for controlled drug release is described and subjected to inspire readers to create novel drug release system. Finally, the conclusions and outlooks of aerogel beads and microspheres for drug delivery are summarized.
There is an array of methodologies to prepare nanocellulose (NC) and its fibrillated form (CNF) with enhanced physicochemical characteristics. However, acids, bases or organosolv treatments on biomass are far from green, and seriously threaten the environment. Current approach to produce NC/CNF from biomass should be revised and embrace the concept of sustainability and green chemistry. Although hydrothermal process, high-pressure homogenization, ball milling technique, deep eutectic solvent treatment, enzymatic hydrolysis etc., are the current techniques for producing NC, the route designs remain imperfect. Herein, this review highlights the latest methodologies in the pre-processing and isolating of NC/CNF from lignocellulose biomass, by largely focusing on related papers published in the past two years till date. This article also explores the latest advancements in environmentally friendly NC extraction techniques that cooperatively use ball milling and enzymatic hydrolytic routes as an eco-efficient way to produce NC/CNF, alongside the potential applications of the nano-sized celluloses.
Sago pith cellulose nanofibril (SPCNF) aerogel derived from sago pith waste (SPW) was successfully produced through three consecutive steps, namely dewaxing and delignification, ultra-sonication and homogenization and freeze drying. The aerogel was characterized using field emission scanning electron microscopy (FE-SEM), Fourier-transform infra-red spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). Results of the analyses collectively showed that lignin & hemicellulose were absent in the SPCNF aerogel product which has a high crystallinity index of 88%. The diameters of individual nanofibril constituents of the SPCNF were between 15 and 30 nm and aspect ratios >1000 were observed. The SPCNF aerogel, with a density measured at 2.1 mg/cm3, was efficient in methylene blue (MB) removal with a maximum MB adsorption of 222.2 mg/g at 20 °C. The adsorption of MB onto the SPCNF aerogel was rapid and found to follow a pseudo-second-order kinetic model with the adsorption isotherm being in congruence with the Langmuir model. The SPCNF aerogel exhibited outstanding MB removal efficacies with 5 mg and 20 mg of SPCNF capable of removing over 90% and almost 99% MB, respectively. The optimized pH value and temperature for MB adsorption were determined as pH 7 and 20 °C.
This work investigates the extraction of cellulose nanocrystals (CNC) from bamboo fibre as an alternative approach to utilize the waste bamboo fibre. In this study, bamboo fibre was subjected to acid hydrolysis for efficient isolation of CNC from bamboo fibre. The extracted CNC's were morphologically, characterized via Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Atomic Force Microscopy (AFM). The energy Dispersive X-rays (EDX) provided the elemental composition of the prepared CNC's and X-ray diffractometer (XRD) exhibited their crystallinity. The physiochemical analysis was done via Fourier Transform Infrared (FTIR); and their thermal analysis was revealed by Thermogravimetric Analysis (TGA) and Differential scanning calorimetry (DSC). As from their morphological investigations, rod like structures of CNC's were observed under SEM analysis with higher carbon content as demonstrated by EDX, while needle shaped CNC's were observed from TEM and AFM studies. Acid hydrolysis for 45 min resulted into higher degree of crystallinity and higher yield of CNC's about 86.96% and 22% respectively. Owing to higher quality of CNC's obtained as a result of efficient and modified techniques, these can find potential usage in nanocomposites for biomedical and food packaging application.
Incorporation of nanocellulose could improve wear resistance of ultra-high molecular weight polyethylene (UHMWPE) for an artificial joint application. Yet, the extremely high melt viscosity of the polymer may constrict the mixing, leading to fillers agglomeration and poor mechanical properties. This study optimized the processing condition of UHMWPE/cellulose nanofiber (CNF) bionanocomposite fabrication in triple screw kneading extruder by using response surface methodology (RSM). The effect of the process parameters-temperature (150-190 °C), rotational speed (30-60 rpm), and mixing time (30-45 min)-on mechanical properties of the bionanocomposites was investigated. Homogenous filler distribution, as confirmed by scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) analysis, was obtained through the optimal processing condition of 150 °C, 60 rpm, and 45 min. The UHMWPE/CNF bionanocomposites exhibited improved mechanical properties in terms of Young's and flexural modulus by 11% and 19%, respectively, as compared to neat UHMWPE. An insignificant effect was observed when maleic anhydride-grafted-polyethylene (MAPE) was added as compatibilizer. The obtained results proved that homogenous compounding of high melt viscosity UHMWPE with CNF was feasible by optimizing the melt blending processing condition in triple screw kneading extruder, which resulted in improved stiffness, a contributing factor for wear resistance.
In skin tissue engineering, a biodegradable scaffold is usually used where cells grow, produce its own cytokines, growth factors, and extracellular matrix, until the regenerated tissue gradually replaces the scaffold upon its degradation. However, the role of non-biodegradable scaffold remains unexplored. This study investigates the potential of a non-biodegradable bacterial nanocellulose/acrylic acid (BNC/AA) hydrogel to transfer human dermal fibroblasts (HDF) to the wound and the resulting healing effects of transferred HDF in athymic mice. Results demonstrated that the fabricated hydrogel successfully transferred >50% of HDF onto the wound site within 24 h, with evidence of HDF detected on day 7. The gene and protein study unveiled faster wound healing in the hydrogel with HDF group and characterized more mature newly formed skin microstructure on day 7, despite no visible differences. These findings give a new perspective regarding the role of non-biodegradable materials in skin tissue engineering, in the presence of exogenous cells, mainly at the molecular level.
In recent days, there is an increasing use of green composites in composite manufacturing, where cellulosic natural fibers have been started using for this purpose. In line with this, a novel cellulose fiber was extracted from the Kigelia africana fruit and its physical, chemical and thermal properties, crystallography and surface morphology analysis were studied and reported in this investigative research paper. The physical analysis revealed the mean tensile strength as 50.31 ± 24.71 to 73.12 ± 32.48 MPa, diameter as 0.507 ± 0.162 to 0.629 ± 0.182 mm and density as 1.316 g/cm³ for the Kigelia africana fiber. The proximate chemical analysis estimated the cellulose percentage to be 61.5 % and the existence of different basic components like cellulose, hemicellulose and lignin are confirmed by Fourier transform infrared spectroscopy analysis. Thermogravimetric analysis establishes the thermal stability of the fiber as 212 ⁰C. The crystallinity index, 57.38 % of the fiber was determined by X-ray diffraction. Surface morphology by field emission scanning electron microscopy reveals the presence of protrusions in fiber which aid in the better adhesion with the matrix in composite manufacturing.
In this study, the microcrystalline cellulose/metal-organic framework 199 hybrid (MCC/MOF-199) was applied as sorbent for the dispersive micro-solid phase-extraction (D-μSPE) of chlorophenols. The D-μSPE method combined with high-performance liquid chromatography- ultraviolet detection (HPLC-UV) was employed to determine of four chlorophenols including 2-chlorophenol (2-CP), 4-chlorophenol (4-CP), 2,3-dichlorophenol (2,3-DCP), and 2,5-dichlorophenol (2,5-DCP) in aqueous. The main parameters of the D-μSPE process that influence the extraction (i.e. the amount of sorbent, elution condition, extraction time, and pH) were investigated and optimized. Based on the outputs, the presence of MCC on the surface of MOF-199 leads to improve the properties of MOF-199 and the MCC/MOF-199 has the highest sorption capacity, durability, and porosity in comparison with MCC and MOF-199. According to the validation study at the optimized conditions, the linearity for the analytes was achieved in the range from 0.1 to 200 ng mL-1 for 2-CP and 4-CP and 0.15 to 200 ng mL-1 for 2,3-DCP and 2,5-DCP with correlation coefficients between 0.9928 and 0.9965. The limits of detection calculated at S/N=3 were in the range of 0.03-0.05 ng mL-1. Besides, the relative standard deviations (RSDs) for three spiking levels (0.2, 10,100 ng mL-1) do not exceed 6.8% and extraction recoveries are between 81.0% and 88.3%. Finally, the D-μSPE-HPLC-UV method was successfully applied to the analysis of CPs in real water samples (mineral, river and wastewater samples) with good recoveries (95.8 to 99.5%) and satisfactory precisions (RSD < 6.8%).
Olive fiber is a renewable natural fiber which has potential as an alternative biomass for extraction of microcrystalline cellulose (MCC). MCC has been widely applied in various industries owing to its small dimensional size for ease of reactive fabrication process. At present study, a serial treatments of bleaching, alkaline and acid hydrolysis was employed to extract OL-BLF, OL-PUF, and OL-MCC respectively from olive stem fiber. In morphology examination, a feature of short micro-crystallite particles was obtained for OL-MCC. The particle size was found gradually reducing from OL-PUF (305.31 μm) to OL-MCC (156.06 μm) due to the disintegration of cellulose fibrils. From physicochemical analysis, most lignin and hemicellulose components had been removed from OL-BLF to form OL-PUF with individually fibril structure. The elemental analysis revealed that highly pure cellulose component was obtained for OL-MCC. Also, the rigidity had been improved from OL-BLF to OL-PUF, while with the highest for OL-MCC with 74.2% crystallinity, endowing it as a reliable load-bearing agent. As for thermal analysis, OL-MCC had the most stable heat resistance in among the chemically-treated fibers. Therefore, olive MCC could act as a promising reinforcing agent to withstand harsh conditions for variety fields of composite applications.
Cellulose nanowhisker (NWC) was extracted by hydrolysing Pennisetum purpureum (PP) fibres with acid and alkali. They were subjected to different periods of acid hydrolysis; 30, 45, and 60 min. NWC morphology and physicochemical properties were characterised by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), particle size analyser, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and thermogravimetric analysis. NWC3, which underwent the longest hydrolysis time, showed the smallest width and length, under TEM. All samples presented a needle-like shape under TEM and AFM; uneven lengths and irregular shapes under FESEM; and a broad range of distribution, with the particle size analyser. All samples exhibited a good crystallinity index (CrI)-72.0 to 74.6%. The highest CrI% corresponded to 60 min of acid hydrolysis. Thermogravimetric analysis showed thermal stability between 310.72 °C and 336.28 °C. Thus, cellulose nanowhisker from PP fibres, have high potential as bio-nanocomposites.
Friction and wear are the main factors in the failure of the piston in automobile engines. The objective of this work was to improve the tribological behaviour and lubricant properties using hybrid Cellulose Nanocrystal (CNC) and Copper (II) oxide nanoparticles blended with SAE 40 as a base fluid. The two-step method was used in the hybrid nanofluid preparation. Three different concentrations were prepared in a range of 0.1% to 0.5%. Kinematic viscosity and viscosity index were also identified. The friction and wear behavior were evaluated using a tribometer based on ASTM G181. The CNC-CuO nano lubricant shows a significant improvement in term of viscosity index by 44.3-47.12% while for friction, the coefficient of friction (COF) decreases by 1.5%, respectively, during high and low-speed loads (boundary regime), and 30.95% during a high-speed, and low load (mixed regime). The wear morphologies results also show that a smoother surface was obtained after using CNC-CuO nano lubricant compared to SAE 40.
Cellulose acetate (CA) is a remarkable biomaterial most extensively used in biomedical applications due to their properties. This review highlighted the synthesis and chemical structure of CA polymer as well as focused on the mechanical, chemical, thermal, biocompatible, and biodegradable properties of electrospun CA nanofibers. These properties are essential in the evaluation of the CA nanofibers and provide information as a reference for the further utilization and improvement of CA nanofibers. Moreover, we have summarized the use of electrospun CA nanofibers in the drug delivery system as a carrier for drugs and classify them according to the drug class, including anti-inflammatory, anticancer, antioxidant, antimicrobial agents, vitamins and amino acids. Our review has been concluded that CA nanofibers cannot wholly be biodegraded within the human body due to the absence of cellulase enzyme but degraded by microorganisms. Hence, the biodegradation of CA nanofibers in vivo has addressed as a critical challenge.