Novel bio-based polyurethane (PU) nanocomposites composed of cellulose nanofiller extracted from the rachis of date palm tree and polycaprolactone (PCL) diol based PU were prepared by casting/evaporation. Two types of nanofiber were used: cellulose nanofibrils (CNFs) and cellulose nanocrystals (CNCs). The mechanical and thermal properties of the nanocomposite films were studied by DMA, DSC, and tensile tests and the morphology was investigated by SEM. Bionanocomposites presented good mechanical properties in comparison to neat PU. While comparing both nanofillers, the improvement in mechanical and thermal properties was more pronounced for the nanocomposites based on CNF which could be explained, not only by the higher aspect ratio of CNF, but also by their better dispersion in the PU matrix. Calculation of the solubility parameters of the nanofiller surface polymers and of the PU segments portend a better interfacial adhesion for CNF based nanocomposites compared to CNC.
The aim of this study is to investigate natural cellulosic fibers extracted from Tridax procumbens plants. The obtained fibers were alkali treated for their effective usage as reinforcement in composites. The physical, chemical, crystallinity, thermal, wettability and surface characteristics were analyzed for raw, and alkali treated Tridax procumbens fibers (TPFs). The test results conclude that there was an increase in cellulose content with a reduction in hemicellulose, lignin, and wax upon alkali treatment. This enhanced the thermal stability, tensile strength, crystallinity, and surface roughness characteristics. The contact angle was also lesser for treated TPFs which prove its better wettability with the liquid phase. The Weibull distribution analysis was adopted for the analysis of the fiber diameter and tensile properties. Thus the considerable improvement in the properties of alkali treated TPFs would be worth for developing high-performance polymer composites.
Ascorbic acid was used for the first time to synthesize cellulose nanoparticles (CNP) extracted from okra mucilage. The physical properties of the CNP including their size distribution, and crystalline structures were investigated. The rheological properties of the cellulose nanofluid (CNF) were compared with the bulk okra mucilage and commercial polymer xanthan. The interfacial properties of the CNF at the interface of oil-water (O/W) system were investigated at different concentrations and temperatures. The effects of the interaction between the electrolyte and ultrasonic were determined. Core flooding experiment was conducted at reservoir condition to justify the effect of the flow behaviour and disperse phase behaviour of CNF on additional oil recovery. The performance of the CNF was compared to conventional EOR chemical. The combined method of ultrasonic, weak-acid hydrolysis and nanoprecipitation were effective in producing spherical and polygonal nanoparticles with a mean diameter of 100 nm, increased yield of 51% and preserved crystallinity respectively. The zeta potential result shows that the CNF was stable, and the surface charge signifies long term stability of the fluid when injected into oil field reservoirs. The CNF, okra and xanthan exhibited shear-thinning and pseudoplastic behaviour. The IFT decreased with increase in concentration of CNF, electrolyte and temperature. The pressure drop data confirmed the stability of CNF at 120°C and the formation of oil bank was enough to increase the oil recovery by 20%. CNF was found to be very effective in mobilizing residual oil at high-temperature high-pressure (HTHP) reservoir condition. The energy and cost estimations have shown that investing in ultrasonic-assisted weak-acid hydrolysis is easier, cost-effective, and can reduce energy consumption making the method economically advantageous compared to conventional methods.
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.
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.
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.
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 predilection of a bi-layered tablet to fail in the interface region after its initial formation in the compaction process reduces its practicality as a choice for controlled release solid drug delivery system. Hence, a fundamental appreciation of the governing mechanism that causes the weakening of the interfacial bonds within the bi-layered tablet is crucial in order to improve the overall bi-layered tablet mechanical integrity. This work has shown that the occurrence of the elastic relaxation in the interface region during the ejection stage of the compaction process decreases with the increase in the bi-layered tablet interface strength. This is believed to be due to the increase in the plastic bonding in the interface region. The tablet diametrical elastic relaxation affects the tablet height elastic relaxation, where the impediment of the tablet height expansion is observed when the interface region experiences a diametrical expansion.
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.
5-Hydroxymethylfurfural (HMF) has been identified as a promising biomass-derived platform chemical. In this study, one pot production of HMF was studied in ionic liquid (IL) under probe sonication technique. Compared with the conventional heating technique, the use of probe ultrasonic irradiation reduced the reaction time from hours to minutes. Glucose, cellulose and local bamboo, treated with ultrasonic, produced HMF in the yields of 43%, 31% and 13% respectively, within less than 10min. The influence of various parameters such as acoustic power, reaction time, catalysts and glucose loading were studied. About 40% HMF yield at glucose conversion above 90% could be obtained with 2% of catalyst in 3min. Negligible amount of soluble by-product was detected, and humin formation could be controlled by adjusting the different process parameters. Upon extraction of HMF, the mixture of ionic liquid and catalyst could be reused and exhibited no significant reduction of HMF yield over five successive runs. The purity of regenerated [C4C1im]Cl and HMF was confirmed by NMR spectroscopy, indicating neither changes in the chemical structure nor presence of any major contaminants during the conversion under ultrasonic treatment. 13C NMR suggests that [C4C1im]Cl/CrCl3 catalyses mutarotation of α-glucopyranose to β-glucopyranose leading to isomerization and finally conversion to HMF. The experimental results demonstrate that the use of probe sonication technique for conversion to HMF provides a positive process benefit.
Acacia mangium, a fast growing tree is widely planted in Malaysia. Converting Acacia wood into nanocellulose could create new value added products for forest-based industry. Nanocrystalline cellulose (NCC) was prepared from Acacia mangium wood pulp via 64wt% sulfuric acid hydrolysis. Prior to acid hydrolysis, Acacia mangium was subjected to pulping followed by bleaching in order to remove non-cellulosic fragments. Acid hydrolysis was carried out on bleached pulp to produce the needle-like NCC with 79% crystallinity and aspect ratio of 26. The resulting NCC was mixed with PVA as a reinforcement material. Incorporation of 2% NCC improved the tensile of the NCC-PVA film by 30%.
A combination between the nanostructured photocatalyst and cellulose-based materials promotes a new functionality of cellulose towards the development of new bio-hybrid materials for various applications especially in water treatment and renewable energy. The excellent compatibility and association between nanostructured photocatalyst and cellulose-based materials was induced by bio-combability and high hydrophilicity of the cellulose components. The electron rich hydroxyl group of celluloses helps to promote superior interaction with photocatalyst. The formation of bio-hybrid nanostructured are attaining huge interest nowadays due to the synergistic properties of individual cellulose-based material and photocatalyst nanoparticles. Therefore, in this review we introduce some cellulose-based material and discusses its compatibility with nanostructured photocatalyst in terms of physical and chemical properties. In addition, we gather information and evidence on the fabrication techniques of cellulose-based hybrid nanostructured photocatalyst and its recent application in the field of water treatment and renewable energy.
Nanocellulose reinforced chitosan hydrogel was synthesized using chemical crosslinking method for the delivery of curcumin which is a poorly water-soluble drug. Curcumin extracted from the dried rhizomes of Curcuma longa was incorporated to the hydrogel via in situ loading method. A nonionic surfactant (Tween 20) was incorporated into the hydrogel to improve the solubility of curcumin. After the gas foaming process, hydrogel showed large interconnected pore structures. The release studies in gastric medium showed that the cumulative release of curcumin increased from 0.21% ± 0.02% to 54.85% ± 0.77% with the increasing of Tween 20 concentration from 0% to 30% (w/v) after 7.5 h. However, the entrapment efficiency percentage decreased with the addition of Tween 20. The gas foamed hydrogel showed higher initial burst release within the first 120 min compared to hydrogel formed at atmospheric condition. The solubility of curcumin would increase to 3.014 ± 0.041 mg/mL when the Tween 20 concentration increased to 3.2% (w/v) in simulated gastric medium. UV-visible spectra revealed that the drug retained its chemical activity after in vitro release. From these findings, it is believed that the nonionic surfactant incorporated chitosan/nanocellulose hydrogel can provide a platform to overcome current problems associated with curcumin delivery.
Dissolved oil palm empty fruit bunch (EFB) cellulose in NaOH/urea solvent was mixed with sodium carboxymethylcellulose (NaCMC) to form a green regenerated superabsorbent hydrogel. The effect of concentration of epichlorohydrin (ECH) as the crosslinker on the formation, physical, and chemical properties of hydrogel was studied. Rapid formation and higher gel content of hydrogel were observed at 10% concentration of ECH. The superabsorbent hydrogel was successfully fabricated in this study with the swelling ability >100,000%. Hydrogel with higher concentration of ECH showed opposite trend by having higher superabsorbent property than that of lower concentration. The covalent bond of COC was observed with Attenuated total reflectance fourier transform infrared (ATR-FT-IR) spectroscopy to confirm the occurrence of crosslinking. The physical and chemical properties of hydrogel were affected by swelling phenomenon. Hydrogel with higher degree of swelling exhibited lower moisture retention and higher transparency. Moreover, the weight of the superabsorbent hydrogel increased with the decrement of pH value of external media (distilled water). This study provided substantial information on the effect of different percentage of ECH as crosslinker on hydrogel basic properties. Furthermore, this study affords correlation of many essential driving forces that affected hydrogel superabsorbent property.
Present study, deals about isolation and characterization of cellulose nanofibers (CNFs) from the Northern Bleached Softwood Kraft (NBSK) pulp, fabrication by hand lay-up technique and characterization of fabricated epoxy nanocomposites at different filler loadings (0.5%, 0.75%, 1% by wt.). The effect of CNFs loading on mechanical (tensile, impact and flexural), morphological (scanning electron microscope and transmission electron microscope) and structural (XRD and FTIR) properties of epoxy composites were investigated. FTIR analysis confirms the introduction of CNFs into the epoxy matrix while no considerable change in the crystallinity and diffraction peaks of epoxy composites were observed by the XRD patterns. Additions of CNFs considerably enhance the mechanical properties of epoxy composites but a remarkable improvement is observed for 0.75% CNFs as compared to the rest epoxy nanocomposites. In addition, the electron micrographs revealed the perfect distribution and dispersion of CNFs in the epoxy matrix for the 0.75% CNFs/epoxy nanocomposites, while the existence of voids and agglomerations were observed beyond 0.75% CNFs filler loadings. Overall results analysis clearly revealed that the 0.75% CNFs filler loading is best and effective with respect to rest to enhance the mechanical and structural properties of the epoxy composites.
Nanocrystalline cellulose (NCC) extracted from lignocellulosic materials has been actively investigated as a drug delivery excipients due to its large surface area, high aspect ratio, and biodegradability. In this study, the hydrophobically modified NCC was used as a drug delivery excipient of hydrophobic drug curcumin. The modification of NCC with a cationic surfactant, cetyl trimethylammonium bromide (CTAB) was used to modulate the loading of hydrophobic drugs that would not normally bind to NCC. The FTIR, Elemental analysis, XRD, TGA, and TEM were used to confirm the modification of NCC with CTAB. The effect of concentration of CTAB on the binding efficiency of hydrophobic drug curcumin was investigated. The amounts of curcumin bound onto the CTAB-NCC nanoparticles were analyzed by UV-vis Spectrophotometric. The result showed that the modified CTAB-NCC bound a significant amount of curcumin, in a range from 80% to 96% curcumin added. Nevertheless, at higher concentration of CTAB resulted in lower binding efficiency.
In this study a cationic surfactant, cetyltrimethylammonium bromide (CTAB), was used as a soft template for in situ chemical polymerization of aniline on the surface of microcrystalline cellulose (MCC). The morphology of the wire-like and porous nanostructure of the resulting composite was highly dependent on the MCC and CTAB concentrations. The effect of the MCC and CTAB concentrations on the electrochemical and morphological properties of the polyaniline (PAni) nanocomposite was studied. Cyclic voltammograms of modified PAni/MCC/CTAB electrode displayed a high current response and the effect of scan rate on the current response confirmed a diffusion controlled process on the surface of the electrode that makes it suitable for sensor applications. The overlapping characteristic peaks of pure PAni and MCC caused peak broadening at 3263 cm-1 in the IR spectra of PAni/MCC/CTAB nanocomposite that revealed the interaction between NH of PAni and OH group of MCC via electrostatic interactions. The addition of MCC to PAni through chemical polymerization decreased the thermal stability of composite compared to pure PAni. Lower crystallinity was observed in the XRD diffractogram, with 2 theta values of 22.8, 16.5, and 34.6 for PAni/MCC, confirming the formation of PAni on the MCC surface.
Microalgal lipid production by Chlorella protothecoides using sugarcane bagasse hydrolysate was investigated in this study. First, maximum glucose and reducing sugar concentrations of 15.2 and 27.0 g/L were obtained in sugarcane bagasse hydrolysate (SCBH), and the effects of different percentages of glucose and xylose on algal cultivation were investigated. Afterwards, SCBH was used as a carbon source for the cultivation of C. protothecoides and higher biomass concentration of 10.7 g/L was achieved. Additionally, a large amount of fatty acids, accounting up to 16.8% of dry weight, were accumulated in C. protothecoides in the nitrogen-limited (0.1-1 mmol/L) culture. Although SCBH inhibited fatty acid accumulation to a certain degree and the inhibition was aggravated by nitrogen starvation, SCBH favored microalgal cell growth and fatty acid production. The present study is of significance for the integration of cost-effective feedstocks production for biodiesel with low-cost SCBH as well as environmentally friendly disposal of lignocellulosic wastes.
The cellulose microfibers (CMF) from water hyacinth (WH) fiber as a filler in sago starch (SS) biocomposites was investigated. The CMF was isolated by pulping, bleaching and acid hydrolysis methods. The addition of CMF in sago matrix was varied i.e. 0, 5, 10, 15 and 20 wt%. Biocomposites were made by using solution casting and glycerol as a plasticizer. The biocomposites were also determined by tensile test, FTIR, X-Ray, thermogravimetric, SEM, and soil burial tests. The results show that the SS15CMF sample has the highest tensile strength of 10.23 MPa than those other samples. Scanning Electron Microscope (SEM) images show that the strong interaction was formed between CMF WH and matrix. Fourier Transform Infra-red (FTIR) indicated that the functional group of biocomposites was a hydrophilic cluster. The addition of CMF WH in sago starch biocomposites lead to the moisture barrier, crystallinity, and thermal stability increased; it is due to the pure sago starch film was more rapidly degraded than its biocomposites.